Topic 11 kinetics

Rate of reaction is the change in the concentration of a reactant or product per unit time

Rate equation shows the relationship between rate of a reaction and the concentration of
reactants.

A -> products
rate= k [A]
k is a rate constant

The order of reaction w.r.t [A] is 1

Partial order of a reaction is the power of which the concentration of the reactant is raised in the
rate equation

* If a reactant does not appear in the rate equation, the reaction is zero order w.r.t that substance

Rate constant is the value independent of concentration and time. It is constant at a fixed
temperature, but varies with different reactions and the presence of catalyst. The unit of k
depends on the overall order of the reaction. The value of k will increase with increasing
temperature.

Overall order of reaction the sum of the powers to which the concentration of the reactants are
raised in the experimental determined rate equation

Rate = k [A]^x [B]^y

Overall order = x + y

Determining Order of Reaction

1. Deducing the Order of Reaction Using Initial Rate Method

- Initial rate is the rate at the start of the reaction, t=0

- The time for a fixed amount of reactant used/ product formed is measured. Since the amount of
reactant used/ product formed is kept constant (initial), rate is proportional to 1/t.

- The rate calculated from the expression is the mean rate over time, not the true initial rate of
reaction
- The initial rate may be calculated from concentration time graphs by calculating the gradient of
tangent at t=0

In a reaction where the rate equation is r=k [A] [B]^2, if [A] is multiplied by 2, rate would X2. If
concentration of B is multiplied by 3, rate would X9. If these changes happen at the same time,
rate would 2 x 9 = X18.

- Initial rate can also be calculated from a clock reaction

a) Sulfur clock reaction

- A large X is drawn on a white tile with a marker pen
- A beaker with sodium thiosulfate and water is placed on top of the X and acid is added to it
- Na2S2O3 (s) + HCl (aq) -> S(s) + H2O (l) + 2NaCl (aq) + SO2 (g)
- The mixture is stirred and the time taken for sulfur (yellow) to be produced to hide the X is
measured
- the experiment is repeated with different amounts of sodium thiosulfate
- The amount of sulfur produced is the same is each experiment so the rate of reaction is
proportional to 1/t
a) Iodine clock reaction
- H2O2 + 2I- + 2H+ -> I2 + 2H2O
- The reaction produces iodine, which then reacts with a fixed quantity of sodium thiosulfate. As
long as there is thiosulfate in the solution, the iodine conc. will be constant as thiosulfate reacts
with iodine and I- ions are oxidised back to I2.
- I2 + 2S2O3 2- -> S4O6 + 2I-
- When all the sodium thiosulfate has been reacted, the next iodine that is produced reacts with
the starch to give an intense blue-black colour
- Higher the concentration of H2O2, faster the release of iodine and shorter the time taken for it
to react with the fixed quantity of sodium thiosulfate so the blue-black colour appears sooner
- A series of experiments is carried out, in which the concentration of H2O2 is varied, while
keeping the conc. of all the other reagents the same. In each experiment the time taken for the
reaction mixture to turn blue is measured
- The amount of iodine produced is the same is each experiment so the rate of reaction is
proportional to 1/t

2. Determining the Order from a Rate-Concentration Graph

- For a rate conc. graph to show the order of a particular reactant, the conc. of that reactant must
be varied while the conc. of other reactants are kept constant and rate should be measured each
time.

3. Deducing the Order by the Continuous Method

- The conc. of one reactant in one reaction mixture is followed throughout the experiment
1) Samples of the reaction mixture are taken at regular time intervals, the reaction in the sample
is quenched and the concentration of the particular reactant is determined by an experimental
technique such as titration
2) The concentration-time graph is plotted to find the half-life for the reaction at different
concentrations

Half life of a reaction is the time taken for the concentration of the reactant to fold to one half of
its initial value

* For this method to work, the concentration of reactants not monitored must be in excess so that
their concentration do not change significantly during the reaction and do not affect the rate of
reaction.
Techniques to Measure the Rate of Reaction

1. Measuring the Volume of Gas Evolved

- When measuring the rate using this technique, either the time taken for a certain volume of a
gas to be collected or the volume of a gas collected within a given time period can be
measured
- The volume of gas produced can also be measured at regular time intervals
a) Collection over water into a measuring cylinder
- Suitable if a large volume of gas is measured (so measurement uncertainty becomes smaller)
- Not good for gases that are very soluble in water
b) Collection Using a Syringe
- Has a greater degree of precision
- Suitable for gases soluble in water (e.g. SO2)
2. Measuring the Change in the Mass of a Reaction Mixture
- Applicable to reactions in which a gas is evolved. The decrease in mass is measured as the
reaction proceed
- Most precise if the gas has a high density e.g. CO2. If not the mass change is small and
measurement uncertainties become significant.

3. Monitoring a Colour Change (Colorimetry)

- If one of the reactants or products is coloured, then the colorimetry can be used to measure the
change in colour intensity of the reaction mixture
- Light absorbance, which is proportional to concentration, is measured by colorimeter at various
time interval with stop watch
- Use a calibration curve to convert absorbance into concentration
4. Analysis by Titration
- Small samples are removed from the reaction mixture using a pipette at regular time intervals
- The reaction in the sample is quenched (stopped or slowing down) by adding the sample to
ice-cold water/ adding another substance that reacts with the reactant or product being titrated

a) CH3COCH3(aq) + I2(aq) -> CH3COCH2I(aq) + H+(aq) + I-(aq)

- This reaction is catalysed by an acid and quenched by NaHCO3 which removes the acid
catalyst
- The remaining iodine is then titrated with sodium thiosulfate solution of known concentration in
presence of starch indicator (brown to blue-black)

b) HCOOCH3(aq) + NaOH(aq) -> HCOONa(aq) + CH3OH(aq)

- NaOH can be titrated with an acid of known concentration in the presence of phenolphthalein
indicator (pink to colourless)

c) BrO3-(aq) + 5Br-(aq) + 6H+(aq) -> 3Br2(aq) + 3H2O(l)

- H+ can be titrated with an akali of known concentration in the presence of phenolphthalein
indicator (colourless to pink)

5. Measuring the Electrical Conductivity

- If there is a change in the number or type of ions in a solution, electrical conductivity can be
measured using a conductivity meter

BrO3-(aq) + 5Br-(aq) + 6H+(aq) -> 3Br2(aq) + 3H2O(l)

- Conductivity decrease indicates the decreasing concentration of reactants
- Conductivity can be converted to concentration by using calibration curve
6. Measuring Optical Activity
- If there is a change in optical activity through the reaction this could be followed in a
polarimeter
Rate Equation and Mechanisms

- If a reaction takes place due to a single collision between the two reacting particles, it can be
described as an elementary reaction
- For an elementary reaction, the rate equation can be deduced directly from the stoichiometric
equation, where the order w.r.t. each reactant will be same as stoichiometric coefficients

Reaction: xA + yB -> C + D
Rate = k [A]^x [B]^y

- A reaction that is not elementary takes place where a series of steps that are collectively called
the mechanism

a) For such a reaction it’s not possible to deduce the rate equation by looking at the
stoichiometric equation
b) Each step has different rate. The slowest step is called the rate determining step
c) The number of moles of each molecule in the rate determining step will be the same as order
of reaction for each molecule
d) If all the steps are added together, they will add up to the overall equation

Rate determining step is the slowest step of a chemical reaction that determines the rate at
which the overall reaction proceeds. The concentration of reactants in a rate determining step are
represented in the rate equation of the same reaction.

1. A + 2B + C -> D + E

step 1: A + B -> X + D slow (rate determining step)

step 2: X + C -> Y fast
step 3: Y + B -> E fast

A + B + X + C + Y + B -> X + D + Y + E
A + 2B + C -> D + E

rate = k [A] [B]^2

- Order w.r.t C is zero as it appears in the mechanism in a fast step after the slow step so it’s not
included in the rate equation

2. NO2(g) + CO(g) -> NO(g) + CO2(g)

step 1: NO2 + NO2 -> NO3 + NO slow

step 2: NO3 + CO -> NO2 + CO2 fast

- The reaction is not elementary because the rate equation does not match overall stoichiometric.
It occurs with several steps.

rate= k [NO2]^2
- rate determining step involves two NO2 molecules and only NO2 is present in rate determining
step

3. A + 2B + C -> D + E

step 1: A + B -> X + D fast

step 2: X + C -> Y slow
step 3: Y + B -> E fast

rate= k [A] [B] [C]

- The intermediate X is not one of the reactants so must be replaced with substances that make
up the intermediate in a previous step
- All reactant species involve either in or before the r.d.s have an effect on the rate of reaction
and appears in the rate equation
4. 2NO(g) + 2H2(g) -> N2(g) + 2H2O(g)

step 1: NO + NO -> X fast

step 2: X + H2 -> Y slow
step 3: Y + H2 -> N2 + H2O fast

rate= k [NO]^2 [H2]

- r.d.s is second step. One molecule of H2 and two molecules of NO appear either before or in
the r.d.s

5. Hydrolysis of Halogeno Primary/ Secondary Alkanes

CH3Cl + OH- -> CH3OH + Cl-

rate= k [CH3Cl] [OH-]

- According to the rate equation the r.d.s involves both the reactants and this is a one step
reaction

- This type of mechanism is called SN2 mechanism (Substitution Nucleophilic Bimolecular)

- r.d.s involves both the reactants and the reaction is overall second order
- Primary/ Secondary halogeno alkanes undergo substitution by SN2 mechanism
6. Hydrolysis of Tertiary Halogeno Alkanes

(CH3)3CBr + OH- -> (CH3)COH + Br-

rate = k [(CH3)3CBr]

- According to the rate equation, r.d.s involves only one species

slow

fast

- This type of mechanism is called SN1 mechanism (Substitution Nucleophilic Unimolecular)

- r.d.s is unimolecular. Reaction is first order so consistent with the rate equation
- Tertiary halogeno alkanes undergo substitution by SN1 mechanism
Effect of Temperature on Rate Constant

Increase in temperature increases:

- the fraction of molecules with energy is equal to or greater than the Ea
- Frequency of collisions due to increased energy of molecules, therefore frequency of successful
collisions increases so does the rate

Activation energy is the minimum energy that colliding particles must possess for a reaction to
occur
- When the colliding particles obtain the Ea, they reach the energy level of the transition state so
that particles can react to form the products

The Arrhenius Equation shows the relationship between the temperature and the rate constant k

k = Ae^(-Ea/RT)

A= a constant known as pre-exponential factor

Ea= Activation energy of the reaction
R= gas constant
T= absolute temperature in kelvin

By taking natural logarithms

k = Ae^(-Ea/RT)
ln k = (-Ea/R)(1/t) + ln A
y = -mx + c

- As Ea gets bigger, the value of k gets smaller

- A large Ea means a slow reaction
- A graph of ln k plotted against 1/t can be used to workout Ea and A. Gradient can be used to
calculate Ea and intercept with the vertical axis can be used to find A
- k is proportional to the rate of reaction so ln k can be replaced by ln rate or ln 1/t
Reaction Profile

A simple one step reaction such as SN2 hydrolysis of primary/ secondary halogenoalkanes has a
single maximum energy.

The reaction profile for SN1 hydrolysis of a tertiary halogenoalkane is a two-step reaction involved
the intermediate R3C+
Catalyst

A catalyst is a substance that increase the rate of a reaction by providing an alternative route with
lower activation energy and remains chemically unchanged at the end of the reaction

1) Homogenous Catalysts
- A homogenous catalyst is in the same phase as the reactants
e.g. Iodination of propanone is catalyzed by the hydrogen ion, H+ (aq)
CH3COCH3 (aq) + I2 (aq) -> CH3COCH2I (aq) + H+ (aq) + I- (aq)

2) Heterogeneous Catalysts
- A heterogenous catalyst is in a different phase to that of the reactants
e.g. Use of solid vanadium oxide (V2O5) in contact process

Use of solid iron in Haber Process

- Solid iron catalyses the reaction between nitrogen gas and hydrogen gas to form ammonia gas.
iron can form an intermediate hydride with hydrogen molecules.
- In the intermediate hydride, hydrogen are held in space between the metal ions in the lattice.
These hydrides then react with nitrogen molecules that are absorbed on to the metal surface.

There are 3 stages in catalysis involving adsorption (the adhesion of particles to the surface of a
solid)

1. Adsorption
- the reactants are first adsorbed onto the surface of the catalyst
2. Reaction
- the reactant molecules are held in positions that enable them to react together
3. Desorption
- The product molecules leave the surface

* These reactions take place on the surface of the catalyst. If the active sites on the catalyst are
already saturated with reactant molecules, increasing pressure won’t have an effect on
heterogenous catalyst

Refer to Core practicals 9a, 9b, 10

Further suggested practicals:

i) the reaction between marble chips and hydrochloric acid (change of mass or change in volume
of gas)
ii) the reaction between magnesium and hydrochloric acid to determine the activation energy
iii) following the rate of the iodine-propanone reaction by a colorimetric method
iv) the catalysis by a cobalt(II) salt of potassium sodium tartrate and hydrogen peroxide
v) the action of the enzyme urease on urea and thiourea
Topic 12A Entropy
A spontaneous (feasible) process takes place on its own without continuous intervention by any
external influence

eg.
Ice melting at 5C -> spontaneous
Water splitting into H2 and O2 at room temp -> not spontaneous

- Most feasible reactions are exothermic because they result in products that are energetically
more stable/ lower energy path
- However, some endothermic reactions are feasible too (e.g. Reaction of ethanoic acid with
ammonium carbonate)
- Therefore, enthalpy is not the only factor that determines the feasibility of a reaction. So we use
another quantity called ‘entropy’, to decide whether a reaction occurs spontaneously

Entropy is a property of matter associated with degree of disorder or randomness of particles and
also with the distribution of quanta of energy between particles
- The greater the freedom molecules have, the greater the entropy as molecules become more
randomly distributed.
- When molecules gain energy, they gain more freedom of movement so there entropy increases
Symbol -> S
Standard entropy symbol -> SΘ (298K, 100kPa)
Unit -> Jmol^-1K^-1

Distribution of Particles

Spreading of molecules during diffusion increases entropy because molecules are randomly
dispersed. When there are more particles, there are more ways of arranging particles.

e.g. The entropy will be more with 0.5 mol of bromine in the gas than with 0.1 mol of bromine
because 0.5 mol contain more gas particles

Distribution of Energy

Energy of a system exists in quanta. Energy quanta are randomly distributed between particles

Molecule 1 Molecule 2

0 4

1 3

2 2

3 1

4 0

When there are more energy quanta, there will be more ways of distributing them between
particles
- When temperature increases, particles of a substance will have more energy.
- There will be more ways of distributing energy quanta
- As a result entropy increases with increasing temperature
* The entropy of a substance increases from solids to liquids to gases
- When a solid increases in temperature, its entropy increases as the particles vibrate more
- Standard molar entropy of a liquid is higher than the solid state because the particles can move
in the liquid state increasing the disorder
- Gases have even higher molar entropies than comparable liquids because particles are free to
move randomly and they are widely spaced. This leads to an increase in disorder in the
gaseous state

- The entropy of a perfect crystal is zero at a temperature of absolute zero (0 K). A perfect
crystal is one with fixed particles which are not moving, rotating or vibrating. The internal
structure is same all the time.

- A decrease in the number of moles on the product side means lower entropy

Q. Explain why the standard molar entropy of diamond is less than that of graphite
A. Diamond has three dimensionally ordered structure while graphite is ordered in 2 dimensions
and has greater degree of freedom between layers (loosely packed)

Q. How does entropy naturally change?

A. Generally entropy change is naturally positive
e.g. a gas spontaneously spreading throughout a room increases its total entropy

Q. Why and how does entropy change during the dissolving of a solid ionic lattice
A. In a solid ionic lattice, ions are initially fixed in place. When the solid dissolves, the ions
dissociate and move in the solution. This freedom of movement increases disorder and increases
entropy.

Q. What are the 3 ways to increase entropy?

A. Increase temperature, change state (from solid to liquid to gas), and increase volume

Total Entropy Change has two components

1. Entropy change of system which consist of reactants and products
2. Entropy change of surrounding consists of container, solvent, air etc

ΔS total = ΔS system + ΔS surrounding

For a reaction to be spontaneous, ΔS total must be positive

Entropy Change of System

The entropy of system will increase (so that it will be positive) when,
- There is a change of state from solid to liquid to gas
- There is an increase in the number of moles from reactants to products
ΔS system = ΣS(products) - ΣS(reactants)

N2(g) + 3H2(g) -> 2NH3(g) SΘ of N2= 191.6 H2= 130.6 NH3= 192.3

ΔS system = 2 x (192.3) - (191.6 + 3 x 130.6) = -198.8 Jmol^-1K^-1

- 4 moles of reactants gives 2 moles of products. Therefore the entropy of system decreases,
resulting in a negative ΔS system
Entropy Change of Surrounding

ΔS surrounding = - ΔH (Jmol^-1) / T (K)

- For exothermic reactions, ΔS surrounding is always positive (entropy of surrounding increases)

- For endothermic reactions, ΔS surrounding is always negative (entropy of surrounding decreases)

Total Entropy Change

- If ΔS total is positive, reaction is thermodynamically feasible

- If ΔS total is negative, reaction is thermodynamically not feasible

Q. Why does water freeze at -5C, not at 5C?

A.
H2O (l) -> H2O (s) ΔH= -6.01 kJmol^-1

-5C (268K) 5C (278K)

ΔS system = ΣS(products) - ΣS(reactants) ΔS system = ΣS(products) - ΣS(reactants)

= 47.9 - 69.9 = -22 Jmol^-1K^-1 = 47.9 - 69.9 = -22 Jmol^-1K^-1

ΔS surr = - ΔH / T ΔS surr = - ΔH / T
= - (- 6.01) x 1000 / 268 = 22.4 Jmol^-1K-1 = - (- 6.01) x 1000 / 278 = 21.6 Jmol^-1K-1

ΔS total = ΔS system + ΔS surrounding ΔS total = ΔS system + ΔS surrounding

= -22 + 22.4 = + 0.4 Jmol^-1K^-1 = -22 + 21.6 = - 0.4 Jmol^-1K^-1

- ΔS total is positive only at -5 C. Therefore, the reaction is thermodynamically feasible at -5C

What Affects Thermodynamical Feasibility?- Total Entropy Change

Thermodynamic feasibility of a reaction depends on,

- The balance between ΔS system and ΔS surr so that even endothermic reactions can occur
spontaneously at room temperature
- Temperature, as higher temperature decreases the magnitude of ΔS surr. So its contribution to
ΔS total is less

- If ΔS surr is negative (for endothermic reactions) it becomes less negative with increasing
temperature
- If ΔS surr is positive (for exothermic reactions) it becomes less positive with increasing
temperature

2Fe2O3(s) + 3C(s) -> 4Fe(s) + 5CO2(g) ΔH= + 468 kJmol^-1 ΔS system= +558 Jmol^-1K^-1

- The entropy of the system increases for this reaction because, two solids have reacted and
formed a solid and a gas, and the number of moles in product side is higher than that in reactant
side

- The reaction is not feasible at room temperature as ΔS total would be - 1012.4 Jmol^-1K^-1, not
thermodynamically feasible
- We can estimate at which the reaction becomes feasible based on two assumptions
1. ΔS system is approximately constant with temperature
2. ΔH remains same

ΔS total = ΔS system + (- ΔH /T)

(ΔS total = 0) ΔS system = ΔH /T
+ 558 = (+468 x 1000) / T
T = 838.7 K

Thermodynamic and Kinetic Stability

Although a reaction is thermodynamically feasible, it still may not be able to occur due to kinetic
factors.
e.g. If a reaction has high activation energy, heat should be provided to start the reaction.
Therefore, this reaction will not occur spontaneously

Examples of kinetic inertness

1) A fuel tank containing petrol and air
2) Mixture of H2 and O2 at room temperature

Another reason to have a deviation from the prediction is non-standard conditions as we predict
the thermodynamic feasibility under standard conditions. If the reaction takes place under non-
standard conditions, prediction may fo wrong.

Thermodynamics tells us what can occur during a process, while kinetics tell us what actually
occurs.

Further suggested practicals:

Investigate chemical reactions in terms of disorder and enthalpy change, including:
i) dissolving a solid, including adding ammonium nitrate crystals to water
ii) gas evolution, including reacting ethanoic acid with ammonium carbonate
iii) exothermic reaction producing a solid, including burning magnesium ribbon in air
iv) endothermic reaction of two solids, including mixing solid barium hydroxide, Ba(OH)2.8H2O
with solid ammonium chloride
Topic 12B Lattice Energy

Lattice Energy

Lattice energy is the exothermic energy change when 1 mol of a solid ionic compound is formed
from its constituent gaseous ions

Na+(g) + Cl-(g) -> NaCl(s) ΔLEH= -780 kJmol^-1

- Lattice energy can be used as a measure of the strength of ionic bonds in different ionic
compounds
- The stronger the ionic bond the more exothermic the lattice energy

Factors affecting the lattice energy

1. Charges on the ions - ionic compounds containing ions with higher charges have stronger ionic
bonds so LE is more exothermic
2. The sum of the ionic radii (inter ionic distance) - smaller ionic radii allows the ions to get closer
increasing the strength of ionic bond so LE becomes more exothermic
3. Type of lattice structure

e.g LE of MgF2 is more negative than that of NaF because Mg2+ has a higher charge and smaller
ionic radius than Na+ so the attraction between ions in MgF2 is stronger so more energy is
released when making MgF2

Standard Enthalpy Change of Atomization ΔatH

ΔatH is the enthalpy change when 1 mol of gaseous atoms is formed from an element in its
standard state under standard conditions

C (s, graphite) -> C(g)

1/2Cl2 -> Cl(g)

Electron Affinity

The first electron affinity of an element is the energy change when each atom in 1 mol of
gaseous atoms gains an electron to form 1 mol of gaseous ions with a charge of -1

O(g) + e- -> O-(g) 1st EA = -349 KJmol^-1

- First EA is exothermic for most of the elements

- Second EA is positive for all elements as energy is required to overcome the repulsion between
the negatively charged ion and the second electron being added

O-(g) + e- -> O2- 2nd EA= +798 kJmol^-1

Ionization Energy

First ionization energy is the enthalpy change when each atom in 1 mol of gaseous atoms
remove an electron to form 1 mol of gaseous ions with a 1+ charge

Mg(g) -> Mg+(g) + e- 1st IE

Mg+(g) -> Mg2+(g) + e- 2nd IE
Standard Enthalpy Change of Formation ΔfH

ΔfH is the enthalpy change when 1 mol of substance is formed from its constituent elements in the
standard state under standard conditions

Na(s) + 1/2Cl2(g) -> NaCl(s)

Born- Haber Cycle

Born-Haber cycle is an energy level diagram used to show overall energy changes that takes place
when an ionic compound is formed from its elements

Electron affinity
of chlorine
Atomization energy
of chlorine

Ionization energy
of sodium

Lattice energy
of sodium chloride
Atomization energy
of calcium

Formation of
sodium chloride

*Hess’s law can be applied to the cycle in order to calculate the lattice energy

Experimental & Theoretical Lattice Energy

- Experimental lattice energy is calculated from Born-Haber cycle. Theoretical lattice energy is
calculated using principles of electrostatics
- Agreement between experimental and theoretical lattice energy indicate the compound is almost
purely ionic.
- A significant different suggests that the compound has a degree of covalent character

*When the covalent character is more, the experimental lattice energy becomes more exothermic
than the theoretical value

The covalence of an ionic compound is due to the polarization. Polarization is the distortion of the
electron density of the anion by the cation.

Polarization will be increased by,

1) High polarising power of the cation
- Higher Charge of the cation
- Smaller radius of the cation
- (Higher charge density of the cation
2) Higher polarisability of the anion
- Higher charge of the anion
- Larger ionic radius of the anion

Q. Will the experimental lattice energy be more negative or less negative than the
theoretical lattice energy? Justify your answer.
A. Experimental lattice energy is more negative due to degree of covalence since Li+ ion polarizes
I- ion.

Q. State and explain how electron affinity values change as you go down Group 7 from
chlorine to iodine
A. Electron affinity becomes less negative as the added electron is further from the nucleus/ the
electron is more shielded from the nucleus

Solubility of Ionic Compounds

Enthalpy of hydration is the enthalpy change when 1 mol of gaseous ion completely dissolves in
water to form an infinitely dilute solution

Na+(g) + aq -> Na+ (aq)

Hydration enthalpies are always exothermic as new attractions are being formed between the ions
and polar water molecules. These forces are called ion-dipole forces/ interactions

Factors Affecting the Magnitude of the Hydration Enthalpy

1. Charge of the ion

- Electrostatic attraction between a higher charged ion& water molecules will be greater than with
a lower charged ion so hydration enthalpy of an ion with a greater charge is more exothermic

2. Radius of the ion

- When the ionic radius decrease, the electrostatic attraction between the ion& water molecules
increases.
- Hence energy released upon hydration increases, so smaller ions have more exothermic
hydration enthalpies

Enthalpy Change of Solution

ΔsolH is the enthalpy change, when 1 mol of a solid ionic compound dissolves in water to form an
infinitely dilute solution

NaCl(s) + aq -> Na+(aq) + Cl-(aq)

*Dissolving of NaCl(s) can be shown by the following Hess’s cycle

ΔLEH + ΔsolH = ΔhydH(Na+) + ΔhydH(Cl-)

Solubility Trends in Group 2

Total entropy change should be considered to predict the solubility of a substance. If total entropy
change is positive, then the substance dissolves

When an ionic solid dissolves into ions, the entropy increases as there is more disorder as solid
changes to solution and number of particles increases. This makes ΔS system positive.
- For salts where ΔsolH is exothermic, the salt will always dissolve at all temperatures, as ΔS total
is always positive
- For salts where ΔsolH is endothermic, the salt may dissolve as long as ΔS system is positive
enough to outweigh the negative value of ΔS surr, making ΔS total positive.

1. Solubility of group 2 metal hydroxide increases on descending the group

- ΔsolH - ΔS surr/ JK^-1mol^-1 S of hydrated cation

Mg(OH)2 3 -10 -138

Ca(OH)2 -16 54 -53

Sr(OH)2 -46 154 -33

Ba(OH)2 -52 174 10

- Enthalpy change of solution become more negative down the group. Therefore, ΔS surr becomes
more positive favouring the solubility
- S of OH- is left out as it is common to all metal hydroxides
- S of the hydrated cation shows the trend in ΔS system. It becomes less negative (i.e more
positive) down the group and this favours the solubility as it increases the entropy of the system
(ΔS system will become more positive)
- As both factors favour an increase in solubility, metal hydroxide become more soluble as you go
down the group

2. Solubility of group 2 sulfate decreases on descending the group

- ΔsolH - ΔS surr/ JK^-1mol^-1 S of hydrated cation

MgSO4 -91 305 -138

CaSO4 -18 60 -53

SrSO4 -9 30 -33

BaSO4 19 -63 10
- S of the hydrated cation shows the trend in ΔS system. It becomes less negative down the group
and this favours the solubility as it increases the entropy of the system. (ΔS system will be more
positive)
- However, enthalpy change of solution become more positive down the group decreasing the ΔS
surr
- The increase in entropy of the hydrated cation is much less than the decrease in the entropy of
the surrounding
- Therefore, group 2 metal sulfates become less soluble as you do down the group

Further suggested practical

Calculate the enthalpy change when a variety of ionic solids are dissolved in water
Topic 13 Chemical Equilibria

A reversible reaction can reach a dynamic equilibrium in a closed container. In a dynamic

equilibrium,
1) the rate of forward reaction is equal to the rate of backward reaction
2) the concentrations of reactants and products remain constant

The composition of reactants and products at the equilibrium is referred to the term, position of
equilibrium

Equilibrium Constant, Kc

The equilibrium constant is a number that expresses the relationship between the amounts of
products and reactants present at equilibrium in a reversible reaction at a given temperature

Kc is a constant at a given temperature and the unit of Kc charges and depends on the equation

N2(g) + 3H2(g) <=> 2NH3(g)

Kc = [NH3]^2 / [N2][H2]^3 = (moldm^-3)^2 / (moldm^-3)^4 = dm^6 mol^-2

Kc for Heterogeneous Reaction

- A heterogenous reaction is one in which at least one of the reactants and/or products is in a
different phase to the others

CaCO3(s) <=> CaO(s) + CO2(g)

Kc = [CO2(g)]

*The concentration term of a solid is constant. Therefore, not included in an equation.

*When water is a reactant, the term [H2O] appears in Kc expression. When water is the solvent,
even if it is a reactant or a product it does not appear because concentration remains constant

Q. Initially there were 1.5 mol of N2 and 4.0 mol of H2 in a 1.5 dm^3 container. At equilibrium
30% of N2 had reacted. Calculate Kc.

A. N2(g) + 3H2(g) <=> 2NH3(g)

N2(g) 3H2 2NH3

initial moles 1.5 4 0

change -0.45 (30% of 1.5) -1.35 (-0.45 x 3) + 0.9 (0.45 x 2)

Eq mol 1.05 2.65 0.9

Eq conc 1.05/ 1.5 = 0.7 2.65/ 1.5 = 1.77 0.9/ 1.5 = 0.6

Kc = [NH3]^2 / [N2] [H2]^3 = [0.6]^2 / [0.7] [1.77]^3 = 0.00927 mol^6 dm^-2

Q. 2 mol of ethanoic acid and 2.00 mol of ethanol are mixed and allowed to reach
equilibrium with ethyl ethanoate and water at 298K. The amount of ethanoic acid at
equilibrium is found to be 0.67 mol. Calculate Kc.

A. CH3COOH(l) + C2H5OH(l) <=> CH3COOC2H5(l) + H2O(l)

CH3COOH(l) C2H5OH(l) CH3COOC2H5(l) H2O(l)

initial moles 2 2 0 0

Change 0.67-2 = -1.33 -1.33 1.33 1.33

Eq mol 0.67 0.67 1.33 1.33

*Because all the reactants and products are in the same ratio, volume gets cancelled out

Kc= [CH3COOC2H5(l)] [H2O(l)] / [CH3COOH(l)] [C2H5OH(l)] = [1.33] [1.33] / [0.67] [0.67] = 3.97

Equilibrium Constant, Kp

If a reaction contains gases, an alternative equilibrium expression can be set up using the partical
pressure of gases instead of concentrations

Partial pressure of an individual gas in a mixture of gases is the pressure the gas would exert if
alone occupied the volume of the whole mixture

N2(g) +3H2(g) <=> 2NH3(g)

PN2 = P x XN2

PN2= partial pressure

P= total pressure
XN2= mole fraction of N2

Mole fraction of a gas = Number of moles of the gas / Total number of moles of all gases

P = P A + P B + PC

mA(g) +nB(g) <=> xC(g) + yD(g)

Kp = (PC(g))^x (PD(g))^y / (PA(g))^m (PB(g))^n

Kp expressions only contain gaseous substances. Any substance with another state is left out.

For a reaction where solids are in equilibrium with gases, pressure is only caused by gaseous

Q. Ammonium hydrogensulfide, NH4HS decomposes when heated and reach equilibrium at

50C. Calculate the partial pressure of both the gasses at this temperature and hence the
total pressure when Kp is 0.142 atm^2.

A. NH4HS(s) <=> NH3(g) + H2S(g)

Kp = 0.142 = (PNH3(g))(PH2S(g))
x^2 = 0.142
x = 0.377 atm (partial pressure of each gas)

Total pressure = 0.377 x2 = 0.754 atm

Relationship Between Total Entropy Change and Equilibrium Constant, K

In a reversible reaction which has reached equilibrium, both forward and backward reactions are
spontaneous so ΔS total is positive in both directions.

ΔS total (forward reaction) = ΔS total (backward reaction)

ΔS total = R ln K

For exothermic reactions,

- ΔH is negative so ΔS surr is positive
- When temperature is increased, ΔS surr becomes less positive so ΔS total decreases
- When ΔS total decreases, the equilibrium constant (K) also decreases. Therefore, for exothermic
reactions, the equilibrium constant decreases with increasing temperature

For endothermic reactions,

- ΔH is positive so ΔS surr is negative
- When temperature is increased, ΔS surr becomes less negative so ΔS total increases
- When ΔS total increases, the equilibrium constant (K) also increases. Therefore, for endothermic
reactions, the equilibrium constant increases with increasing temperature

Predicting the Direction of Change

xA + yB <=> mC + nD
Kc = [C]^m [D]^n / [A]^x [B]^y

Right hand side of the expression is called reaction quotient (Q), also called concentration term

1) Q = Kc
- The system is in quilibrium
2) Q > Kc
- System is not in equilibrium
- The system will reduce the quotient by converting products to reactants (increasing the
denominator) until Q = Kc
- POE will shift to left
3) Q < Kc
- System is not in equilibrium
- The system will increase the quotient by converting reactants to products (increasing the
numerator) until Q = Kc
- POE will shift to right
Effect of Changing Conditions

* Kc and Kp only change with temperature

1. Effect of Changing Temperature on Kc, Kp, POE

- Both POE and the value of Kc and Kp will change if temperature is altered
Exothermic
- An increase in temperature will decrease Kc and Kp
- Now the quotient is bigger than the new value of K (system is no longer in Eq)
- To restore the Eq, the value of Q decreases until it becomes equal to new K (this is done by
decreasing the numerator)
- Therefore, POE shifts to left, making more reactants
* When temperature increases, POE shifts to left because forward reaction is exothermic
Endothermic
- An increase in temperature will increase Kc and Kp
- Now the quotient is smaller than the new value of K (system is no longer in Eq)
- To restore the Eq, the value of Q increases until it becomes equal to new K (this is done by
increasing numerator)
- Therefore, POE shifts to right, making more products
* When temperature increases POE shifts to right because reaction is endothermic

2. Effect of Catalyst
- A catalyst has no effect on Kc, Kp and POE
- But it will speed up the rate at which the Eq is achieved
* It doesn’t affect POE because it speeds up the rate of forward and backward reactions by the
same rate

3. Effect of Changing Concentration on the Value of Kc, and POE

- Changing con. has no effect on the value of Kp and Kc but POE will shift
N2 (g) + 3H2 (g) <=> 2NH3 (g)
Kc = [NH3]^2 / [N2] [H2]^3

- If the conc. of a reactant is decreased, Kc remains unchanged, Q increases

- To restore the Eq, the value of Q decreases until it becomes Eq to Kc
- The POE shifts to the left making products
* If the volume of the reaction mixture is increased, the concentration of all reactants and
products decreases and vice versa

Q. Explain the effect on Kc and the number of moles of NO at Eq if the volume of the vessel
is doubled.

2NOCl (g) <=> 2NO(g) + Cl2(g)

Kc = [NO(g)]^2 [Cl2(g)] / [NOCl(g)]

A. Kc remains constant as temperature is unchanged. When volume doubles, the conc. of

reactants and products become half. The value of numerator decreases more than the value
of denominator. Therefore, the value of reaction quotient decreases and become less than Kc
(so the system is no longer in Eq). To restore the Eq, the quotient increases until it equals Kc.
POE shifts to right, making more moles of NO

4. Effect of Changing Pressure or Volume of the Container on Kp and POE

- The POE will change with change in pressure but Kp remains constant
N2 (g) + 3H2 (g) <=> 2NH3 (g)
Kp = [PNH3(g)]^2 / [PN2(g)] [PH2(g)]^3 = p^2 / p^4

- Increasing pressure or decreasing volume does not affect Kp

- The increased pressure increases the value of denominator more than the value of numerator.
Therefore, the reaction quotient decreases and become less than Kp (system no longer in Eq)
- To restore the Eq, the value of quotient increases until it becomes Eq to Kp
- Therefore, POE shift to right making more products
* When pressure is increased, POE shift to the right as there are fewer moles of gases on the right
hand side so the yield of ammonia increased.
Q. Explain the effect of increased pressure in this example

H2 (g) + I2 (g) <=> 2HI (g)

- An increased pressure does not change Kp

- The increased pressure increases the value of denominator and numerator by the same factor.
Therefore, the value of quotient does not change
- Neither Kp nor the reaction quotient has altered. Thus, Kp = Q so the system is still in Eq
- If there are same number of gas molecules on both sides, the value of Q is not affected by a
change in pressure so the system is still in Eq

Relationship Between Kc, Kp and POE

Kc > 1
- POE is well over to the product side. Product predominates in an Eq
Kc < 1
- POE is over to the reactant side. Reactants predominate in an Eq
Kc = 1
- Equal amounts of reactants and products
Kc < 10^-10
- Reaction does not go
Kc > 10^10
- Reaction goes to completion
Partition Coefficient

Partition coefficient is the ratio of the equilibrium concentrations of a dissolved substance in

reaction consisting of two largely immiscible solvents

I2 (aq) <=> I2 (hexane)

Kc = [I2 (hexane)] / [I2 (aq)]
Kc = partition coefficient

Method
1. Iodine was shaken with a mixture containing 10.0 cm^3 of hexane and 100 cm^3 of water and
allowed to reach Eq. The layers separated and each was titrated against 0.0200 moldm^-3
sodium thiosulfate solution
I2 + 2S2O3 2- -> S4O6 2- + 2I-

2. The aqeous layer required 8.9 cm^3 of sodium thiosulfate solution and hexane layer required
76 cm^3
3. Use this information to calculate the number of moles of sodium thiosulfate required to
neutralize iodine in each layer. Hence find the number of moles of iodine (mol ratio) and its conc.
4. Calculate the value of Kc, the partition coefficient

Further suggested practicals:

i) the reaction of ethanol and ethanoic acid (this can be used as an example of the use of ICT to
present and analyse data)
ii) the equilibrium Fe2+(aq) + Ag+(aq) Fe3+(aq) + Ag(s)
iii) the distribution of ammonia or iodine between two immiscible solvents
iv) the thermal decomposition of ammonium chloride
v) the effect of temperature and pressure changes in the system 2NO2 N2O4
Topic 14 Acid Base Equilibria

According to Bronsted-Lowry,
- Acid is a proton donor
- Base is a proton acceptor
Conjugate Acids and Bases

When an acid donates a proton, the species formed is the conjugate base of the acid
Acid - H+ -> Conjugate Base

When a base accepts a proton, the species formed is the conjugate acid of the base
Base + H+ -> Conjugate Acid

A substance that behaves as an acid or a base is described as amphoteric

e.g Water

Monoprotic, Diprotic Acids and Bases

Acids that can donate a maximum of one, two or three protons are called monoprotic, diprotic or
triprotic acids respectively
- They are also called monobasic, dibasic or tribasic acids
e.g. monoprotic acid- HCl, HNO3 diprotic acid - H2SO4

Bases that can accept one, two or three protons are called monoprotic, diprotic or triprotic bases
respectively
- They are also called monoacidic, diacidic or triacidic bases
e.g monoprotic base - Cl- diprotic base - CO3 2-

Strong Acids, Weak Acids, Strong Bases, Weak Bases

1. A strong acid is one that completely dissociate in aqueous solution forming H+ ions
HCl (aq) -> H+ (aq) + Cl-(aq)

2. A weak acid is one that only partially dissociate (in less than 10%) in aqueous solution. Partial
dissociation is represented by using reversible arrows
CH3COOH (aq) <=> CH3COO- (aq) + H+ (aq)

3. A strong base is one that completely dissociates in aqueous solutions to form OH- ions
NaOH (aq) -> Na+ (aq) + OH- (aq)

4. A weak base is one that partially dissociates in aqueous solution to form OH- ions
NH3 (aq) + H2O (l) <=> NH+4(aq) + OH- (Aq)
pH and Hydrogen Ion Concentration

pH = -log10 [H+]

pH of an aqueous solution is the reciprocal of the logarithm to the base 10 of hydrogen ion
concentration measured in moldm^-3

[H+] = 10^-pH

[H3O+] 10 1 10^-1 10^-2 10^-3 … 10^-14

pH -1 0 1 2 3 … 14
A change in one unit of pH scale corresponds to a tenfold change in the concentration

Ionic Product of water, Kw

Water dissociates very slightly as follows

H2O (l) <=> H+(aq) + OH-(aq)

K = [H+(aq)] [OH-(aq)] / [H2O(l)]

K [H2O(l)] = [H+(aq)] [OH-(aq)]
Kw = [H+(aq)] [OH-(aq)]
Kw = ionic product of water

Kw is the product of the concentration of hydrogen ions and hydroxide ions both measured in
moldm^-3

* The value of Kw at 298k is 1x10^-14 mol^2dm^-6

298K => Kx = [H+(aq)] [OH-(aq)] = 1 x 10^-14

In a neutral solution/ pure water
[H+(aq)] = [OH-(aq)]
[H+(aq)]^2 = 1 x 10^-14
[H+(aq)] = 1 x 10^-7

pH = -log10 [1 x 10^-7]
pH = 7

Sometimes Kw is quoted as pKw value

pKw = -log10 [Kw] Kw = 10^-pKw

pH = -log10 [H+] [H+] = 10^-pH
pOH = -log10 [OH-] [OH-] = 10^-pOH

For any aqueous solution at 298K

[H+(aq)] [OH-(aq)] = Kw = 1 x 10^-14
-log10 [H+] + -log10 [OH-] = -log10 [Kw]
pH + pOH = pKw = 14

Kw and Its Temperature Dependence

Kw varies with temperature

- The dissociation of water is endothermic, so increasing the temperature will push the equilibrium
to the right, giving a larger conc. of H+ ions and OH- ions. Therefore, the value of Kw increases
with increasing temperature so the pH value of water (pure water) decreases with increasing
temperature
At 273k, Kw = 1.14 x 10^-15 moldm^-3
At 298k, Kw = 1 x 10^-14 moldm^-3
At 303k, Kw = 1.47 x 10^-14 moldm^-3

At 273k At 303k
Kw = 1.14 x 10^-15 moldm^-3 Kw = 1.47 x 10^-14 moldm^-3

Kw = [H+(aq)] [OH-(aq)] Kw = [H+(aq)] [OH-(aq)]

for pure water (neutral), for pure water (neutral),

Kw = [H+(aq)]^2 Kw = [H+(aq)]^2
1.14 x 10^-15 = [H+]^2 1.47 x 10^-14 = [H+]^2
[H+] = 3.38 x 10^-8 [H+] = 1.21 x 10^-7
pH = -log10 [3.38 x 10^-8] pH = -log10 [1.21 x 10^-7]
pH = 7.47 pH = 6.92
* Higher the temperature, lower the pH value of pure water

pH of Strong Acid

A strong acid dissociates completely in aqueous solution

HX (aq) -> H+ (aq) + X- (aq)

0.1 0.1 0.1

pH of Aqueous Solutions of Strong Bases

For bases you are normally given the concentration of the hydroxide ions
Strong bases completely dissociate into ions

NaOH (aq) -> Na+ (aq) + OH- (aq)

0.1 0.1 0.1

Kw = [H+(aq)] [OH-(aq)]
1 x 10^-14 = [H+] [0.1]
[H+] = 10^-13
pH = -log10 [10^-13] = 13

or

pH + pOH = pKw = 14

pH + -log10 [OH-] = -log10 [10^-14]

pH + 1 = 14
pH = 13

pH of Weak Acid

A weak acid dissociates partially in aqueous solutions

HA (aq) <=> H+ (aq) + A- (aq)

Applying the Eq law to the above Eq mixture

Ka = [H+(aq)] [A-(aq)] / [HA (aq)]

Ka = acid dissociation constant

* The larger the Ka, stronger the acid (more dissociation in the solvent)
pKa = - log [Ka]
Ka = 10^-pKa
In calculations involving pH of weak acids, the following two assumptions are made
1) [H+] due to ionization of water is negligible (all H+ ions come from the dissociation fo the acid,
so [H+] = [A-])
2) Dissociation of the weak acid is negligible, so [HA(aq)] equilibrium = [HA(aq)] initial

Ka = [H+(aq)] [A-(aq)] / [HA (aq)]

Ka = [H+(aq)]^2 / [HA(aq)] initial

pH of Weak Bases

A weak base is partially ionized in water

NH3 (aq) + H2O (aq) <=> NH4+ (aq) + OH- (aq)

Kb = [NH4+(aq)] [OH- (aq)] / [NH3 (aq)]

pH of a Dibasic Acid

For a dibasic acid such as H2SO4, it maybe thought that H+ ion concentration is double that of
acid (0.1M sulfuric to have 0.2M H+)

This is not so. Sulfuric acid dissociates in two steps,

Strong acid H2SO4 (aq) -> HSO4- (aq) + H+ (aq)

0.1 0.1 0.1

Weak acid HSO4- (aq) <=> H+ (aq) + SO4 2- (aq)

- The second ionization is significantly reduced by the high concentration of H+ ions produced in
the first ionization. The H+ from the second ionization contributes so little to H+ concentration.

expected pH = - log [0.1 x 2] = 0.69

real pH = 0.98

Dilution of Solutions
Conc / moldm^-3 pH of Strong Acid pH of Weak Acid

1.0 0 2.38

0.1 1 2.88

0.01 2 3.38

0.001 3 3.88
- When strong acids/ bases are diluted, the pH change b one unit for each 1o fold dilution
- When weak acids/ bases are diluted, pH changes b a factor of about 0.5 for each 10 fold
dilution

Q. Calculate new pH when 500cm^3 of 0.15 moldm^-3 of HCl is mixed with 500 cm^3 of
water

A. HCl New
V = 500cm^3 V = 1000 cm^3
c = 0.15 moldm^-3 c =?
pH = - log [0.15]

C1V1 = C2V2
C2 = 0.075

pH = - log [0.075] = 1.12

Comparing Solutions from pH Measurements

a) The higher the value of pH, the weaker the acid

b) The higher the value of pH, the stronger the base

c) Salt Solutions
i) Salt of a strong acid and strong base (pH 7)
NaCl (aq) -> Na+ (aq) + Cl- (aq)

ii) Salt of a strong acid and weak base

NH4Cl (aq) -> NH4+ (aq) + Cl- (aq)
NH4+ (aq) + H2O (l) <=> NH3 (aq) + H3O+ (aq) pH < 7

Ka = [NH3 (aq)] [H3O+ (aq)] / [NH4+ (aq)]

iii) Salt of a weak acid and strong base

CH3COOH + NaOH -> CH3COONa + H2O
CH3COONa -> CH3COO- (aq) + Na+ (aq)

CH3COO- + H2O <=> CH3COOH + OH- pH > 7

- ethanoate hydrolyzes in water producing OH- ions which makes the solution alkaline
iv) Salt of a weak acid and weak base
pH depends on Ka and Kb value of acid and base

Ka > Kb pH < 7
Ka < Kb pH > 7
Ka = Kb pH = 7

Buffer Solution

A buffer solution is one that resists a change in pH on the addition of a small amount of acid
and/ or an alkaline

1. Acid Buffer Solution

- This consists of a mixture of a weak acid and its salt of similar concentration (weak acid and its
conjugate base)
CH3COOH, CH3COONa

- Consider weak acid HA, and its salt NaA

NaA -> Na+ + A-
HA <=> H+ + A-

Ka = [H+(aq)] [A-(aq)] / [HA (aq)]

Assumptions made during calculations

1) H+ conc. due to ionization of water is negligible/ all H+ ions come from the dissociation of the
weak acid
2) Dissociation of the weak acid is negligible. Therefore, [HA(aq)] equilibrium = [HA(aq)] initial
3) Since the dissociation of the weak acid is negligible, A- conc. from the totally ionized salt is
much greater. [A-(aq)] equilibrium = [salt (aq)] initial

- So we can simplify the equation

Ka = [H+(aq)] [salt (aq)] initial / [HA(aq)]initial
Explain the buffer action of a mixture containing ethanoic acid and sodium ethanoate
CH3COONa -> CH3COO- + Na+
CH3COOH <=> CH3COO- + H+

1) The mixture contains a large reservoir/ high concentration of ethanoic acid and sodium
ethanoate
2) When a small amount of an acid is added, CH3COO- reacts with H+ ions forming ethanoic
acid so removes H+ from solution
CH3COO- + H+ -> CH3COOH
3) When a small amount of an alkali is added, the acid CH3COOH reacts with OH- ions to form
ethanoate and water so removes OH- form solution
CH3COOH + OH- -> CH3COO- + H2O
4) The ratio ethanoic acid to ethanote does not change significantly when a small amount of an
acid or an alkali is added. Therefore, pH remains fairly constant.

Q. Calculate the pH of a buffer solution made by adding 1.42g of potassium methanoate into
50cm^3 of 0.111 moldm^-3 solution of methanoic acid. Ka = 1.78 x 10^-4 moldm^-3

A. CHOOH <=> CHOO- + H+

CHOOK -> CHOO- + K+

Ka = [CHOO-] [H+] / [CHOOH]

mole of CHOOK = 1.42/ (39.1 + 16 x 2 +12 +1) = 0.016884 mol

[CHOOK] = 0.016884 / 50x10^-3 = 0.3376 moldm^-3
[CHOOH] = 0.111 moldm^-3
[H+] = Ka [CHOOH] / [CHOO-] = 1.78 x 10^-4 x 0.111 / 0.3376 = 5.85 x 10^-5

pH = - log [5.85 x 10^-5] = 4.233

2. Alkaline Buffer Solution

- This consists of a mixture of a weak base and its salt of similar concentration (weak base and
its conjugate acid)
NH3, NH4Cl

- Consider a buffer solution made up of ammonia and ammonium chloride. The most convenient
equilibrium to consider is

NH4+ (aq) + H2O (l) <=> NH3 (aq) + H3O+(aq)

Ka = [NH3(aq)] [H3O+(aq)] / [NH4+(aq)]

[H3O+] = Ka x [NH4+(aq)] / [NH3 (aq)]

Explain the buffer action of the above solution

1) The mixture contains a large reservoir of ammonia and ammonium chloride
2) When a small amount of an acid is added, ammonia reacts with H+ forming ammonium ions
NH3 + H+ -> NH4+
3) When a small amount of an alkali is added, ammonium reacts with OH- ions forming ammonia
NH4+ + OH- -> NH3 +H2O
4) The ratio of ammonia conc. to ammonium conc. does not change significantly when a small
amount of an acid or an alkali is added. Therefore, pH remains fairly constant

Q. In what proportion should we mix 0.1 moldm^-3 ammonia and ammonium chloride to
obtain a buffer of pH 9.8? Ka = 5.62 x 10^-10 moldm^-3

A. [H+] = 10^-9.8 = 1.5849 x 10^-10

[NH3(aq)] / [NH4+(aq)] = Ka / [H3O+] = 5.62 x 10^-10 / 1.5849 x 10^-10 = 3.55

We have to mix the solutions in a ratio by volume 3.55 ammonia to 1 ammonium chloride
Henderson Hasselbalch Equation to Calculate the pH of a Buffer Solution

pH = pKa + log ( [Salt] / [Weak Acid] )

= - log [1.8 x 10^-5] + log ( 0.04/0.08 ) = 4.74 - 0.301 = 4.44

How to make a Buffer Solution with a Required pH

Q. Calculate the mass of sodium ethanoate Q. Calculate the relative volumes of one mole
that has to be added to 100cm^3 of 0.1 per dm^3 solution of ethanoic acid and one
moldm^-3 solution of ethanoic acid to make mole per dm^3 solution of sodium ehtanoate
a solution with pH 4.38.
Ka = 1.8 x 10^-5
CH3COOH pH = 4.0
c = 0.1M
V = 100cm^3 CH3COONa -> CH3COO- + Na+
pH = 4.38 CH3COOH <=> CH3COO- + H+
Ka = 1.8 x 10^-5 Ka = [CH3COO-] [H+] / [CH3COOH]

[H+] = 10^-4.38 = 4.169 x 10^-5 (1) [H+] = 10^-4 M

mol of CH3COOH = 0.1 x 100 x 10^-3 = 0.01 [CH3COOH] / [CH3COO-] = 10^-4 / 1.8 x 10^-5
[CH3COOH] = 0.01 / 100 x 10^-3 = 0.1 = 5.6

CH3COOH <=> CH3COO- + H+ (2) 1M CH3COOH : V1

Ka = [CH3COO-] [H+] / [CH3COOH] 1M CH3COONa : V2

[CH3COO-] = 1.8 x 10^-5 x 0.1 / 4.169 x 10^-5 mol of CH3COOH = 1 x V1 = V1

= 0.0432 M [CH3COOH] = V1 / (V1 + V2)

mol of CH3COO- = 0.0432 x 100 x 10^-3 mol of CH3COONa = 1 x V2 = V2

n = 4.32 x 10^-3 [CH3COONa] = V2 / (V1 + V2)

Mass of salt = 0.00432 x 82 = 0.35g [CH3COOH] / [CH3COO-] = V1 / V2 = 5.6

When V1 = 5.6 cm^3, V2 = 1 cm^2

Acid Base Titrations and pH Curves

Equivalence point is when the acid and base have reacted together in the exact proportion as
given by the stoichiometric equation

* pH of the solution at the equivalence point depends on the combination of the acid and base
used, because the salt formed during the reaction may undergo hydrolysis to give an acidic or
alkaline solution

A titration curve shows how the pH of a solution varies gradually as the reagent in the burette is
added
1. Titration of a Strong Acid with a Strong Base
NaOH + HCl -> NaCl +H2O

Vertical part: 3 - 11

Equivalence point: 7

(When they are in the same conc.)

2. Titration of a Weak Acid with a Strong Base

CH3COOH + NaOH -> CH3COONa + H2O

buffer range

Vertical Part: 7 - 11

Equivalence point: 8.5 to 9

pH starts approximately between 2.5 - 3

- At the equivalence point, the solution contains a salt of a strong base and a weak acid
- This salt undergo hydrolysis producing OH- ions
CH3COOH + NaOH -> CH3COONa + H2O
CH3COO- + H2O -> CH3COOH + OH-
- Therefore, the pH is greater than 7 and the solution is alkaline at the equivalence point
- When a weak acid is titrated against a strong base, there is a fairly rapid change of about 1.5
pH units when the strong base is first added
- Then the buffer range begins. Over this range there is a considerable concentration of both
weak acid and its salt (conjugate base). This mixture displays a buffer action.
- In the above titration, the buffer solution contains ethanoic acid and sodium ethanoate in large
amounts. So the addition of alkali has relatively little effect on the pH of the solution in this
range
- Therefore, the change in pH is gradual in the buffer region. In this part of the graph the pH
changes slowly. This part of the graph is flat or horizontal

- At half equivalence point (v = 12.5cm^3) for alkali added to acid, mixture contains the weak
acid CH3COOH and its salt CH3COONa in similar concentration. The mixture at this point is a
buffer solution as stated before.

At half equivalence point

CH3COOH <=> CH3COO- + H+ Ka = 10^-4.8 = 1.58 x 10^-5
Ka = [CH3COO-] [ H+] / [CH3COOH]

[CH3COO-] = [CH3COOH]
Ka = [H+]
pKa = pH
pH = 4.8

3. Titration of a Strong Acid with a Weak Base

NH3 + HCl -> NH4Cl

buffer range

buffer range

Vertical part: 3 to 7

Equivalence point: 5.5

- At the equivalence point, the solution contains a salt of a strong acid and a weak base
NH3(aq) + HCl (aq) -> NH4Cl (aq)
- NH4+ reacts with water/ hydrolysed by water to product H3O+ ions
NH4 (aq) + H2O (l) <=> NH3 (aq) + H3O+
- Therefore, the pH of the solution is less than 7 due to H3O+ formed
- At half equivalence point of acid added to alkali, the mixture contains weak base ammonia and
its salt ammonium chloride in similar concentrations
- Therefore, the mixture acts as a buffer solution
4. Titration of a Weak Acid with a Weak Base
CH3COOH + NH3 -> CHCOONH4

The shape of the curve doesn’t show any

sharp change in pH

Titration Curves with Diprotic Acids

A diprotic acid dissociates in two stages

1) H2X -> HX- + H+
2) HX- -> X 2- + H+

Because of the successive dissociations, the titration curves of diprotic acids have two
equivalence points

Consider the acid-base reaction between a diprotic acid and base NaOH
- At the first equivalence point, all H+ from the first dissociation have reacted with NaOH. From
the beginning of the reaction to the first equivalence point
NaOH + H2CO3 -> NaHCO3 + H2O
- From the first equivalence point to the second equivalence point
NaOH + NaHCO3 -> Na2CO3 + H2O
- At the second equivalence point, all H+ ions from both reactions have reacted with NaOH
Overall reaction: 2NaOH + H2CO3 -> Na2CO3 + 2H2O

* The volume of NaOH added for second reaction is exactly the same as the first, because the
number of moles of NaOH which react with the NaHCO3 is the same as that reacting with the
H2CO3
Acid Base Indicators

An acid base indicator is ether a weak acid or a weak base

Most indicators are weak acids and they dissociate in aqueous solutions as follows

HIn <=> H+ + In-

acid conjugate base
colour A colour B

- The acid has a different colour to its conjugate. They change colour when they lose or gain
protons

- In an acid solution, the large H+ ions concentration will make the equilibrium to shift to left.
Therefore, colour A predominates in acidic solution
- In an alkaline solution, OH- ions will react with H+ ions forcing the equilibrium to shift to right.
Therefore, colour B predominates in alkaline solution

The end point of a titration is defined as the point when the colour of the indicator changes

The pH at which different indicators change colour can be determined by their pKIn values

KIn = [H+] [In-] / [HIn]

At end point, [In-] = [HIn]

KIn = [H+]

pKIn = pH

*When pH of the medium equals pKIn of indicator, it will change its colour

- Therefore, the best indicator is the one whose pKIn value is as close as possible to the pH at
the equivalence point/ pKIn is the mid point of vertical path
- An indicator will work if the pH range lies within the vertical path of the titration curve
- Otherwise, the indicator colour will change either before equivalence point or at some value
after the equivalence point

- When a weak acid reacts with a weak base, there is no sharp change in pH in the titration
curve, so neither indicator is suitable

Importance of Buffer Solutions

Buffer in food
- Spoilage of food by microorganisms depends greatly on the pH value of the food
- Most microorganisms thrive when the pH of their surrounding is close to neutral
- Buffer capacity is a measure of the amount of acid or bae required to change significantly the
pH of food. The more protein there is in the food, the higher is its buffer capacity.
- This is because the amino acids present have both acidic and basic properties so it takes
longer for the pH of the food to change enough for the bacteria to stop multiplying
- Bacteria and moulds can also produce waste products that act as poison and toxins cuasing
ill-effects

- Most processed food, such as jams, contain buffer system such as citric acids and sodium
citrate which help to maintain a pH within a range where growth of microorganisms is very slow
or non-existant
Buffer in Cells and in Blood
- pH of blood plasma needs to be in the range 7.35-7.45 to prevent enzyme denaturation and cell
damage
- pH of blood is mainly controlled by carbonic acid - hydrogen carbonate buffer mixture (H2CO3
and HCO3- buffer mixture)
H2CO3 (aq) <=> HCO3- (aq) + H+ (aq)
- If [H+] in blood increases, equilibrium moves to left as [H+] reacts with HCO3- ions
- If [OH-] in blood increases, OH- reacts with H+ so the equilibrium moves to right as H2CO3
molecules ionize to increase [H+] and restore the pH to its normal level

The above buffer is coupled with the respiratory system of the body
CO2(g) + H2O (g) <=> CO2 (aq) + H2O (aq) <=> H2CO3 (aq) <=> HCO3- (aq) + H+ (aq)

- If [H+] increases, the concentration of CO2 in blood increases

- CO2 leaves blood in the lungs and is then exhaled, thus maintaining the normal pH
Refer to Core Practical 11

Further suggested practicals:

i) carry out the measuring of the pH of solutions mentioned in 14.13
ii) obtain data to draw titration curves mentioned in 14.15 (which gives an opportunity to use data
loggers)
iii) analysis of vinegar
Topic 15A Chirality

Isomerism

Isomers

Structural Isomers Stereo Isomers

- Compounds with the same - Compounds with the same structural
molecular formlae but with formulae but atoms or groups are arranged
different structural formulae differently in three dimensions

Geometric Isomers Optical Isomers

- There is restricted rotation around the C=C - non-superimposable images of each other
double bond - Has a chiral centre, which refers to a
- There are 2 different groups/ atoms attached carbon atom in a molecule that is
to both C atoms of the double bond attached to four different atoms or groups

Chirality and Optical Isomers

Chiral centre b (aka asymmetric carbon atom) in a molecule is the one that allows it to exist as
non-superimposable

- These two structures have a chiral centre and they are a mirror image of each other
- Two compounds that are optical isomers of each other are called enantiomers

Polarimeter

Light from a given source vibrates in all possible planes at right angles to the direction of travel.
Unpolarised light is converted to plane polarized light when passing through a polariser. Plane
polarised light has oscillations in only one plane, right angle to the direction of travel
Method:
- Polariser is used to measure the amount of optical activity/ measure the angle of rotation
caused by a substance
- A monochromatic light (light with only one colour) is passed through a polariser
- It converts unpolarised light into vertically plane polarised light
- The plane polarised light is then passed through a sample of substance in solution
- If the substance is optically active, because it contains an enantiomer, then the plane of
polarisation of plane polarised light will be rotated so that it is no longer vertical
- The angle of rotation is measured by an analyzer
- If the rotation is clockwise, the angle is quoted as a positive value and the substance is
described as a dextrorotatory enantiomer isomer
- If the rotation is anti-clockwise, the angle is quoted as a negative value and the substance is
described as a laevorotatory enantiomer isomer

A substance shows optical activity if it rotates the plane of plane polarised light

* Enantiomers have similar physical and chemical properties but, they rotate the plane of
polarisation of plane polarised light in opposite directions in equal angles

Racemic Mixture

A racemic mixture is a mixture that contains equal amounts of two enantiomers (dextrorotatory
and laevorotatory).
- Two enantiomers in racemic mixture have equal but opposite effects on plane-polarised light.
- Therefore, a racemic mixture does not rotate the plane of plane polarised light (clockwise
rotation of one enantiomer is cancelled by the anti-clockwise rotation of the other enantiomer)
- The racemic mixture has no optical activity
* It is not possible to distinguish between a substance that has no optical activity and one that
has optically active enantiomers in similar amounts (racemic mixture) whose effects cancel out
without knowing anything about the sample

Optical Activity and Reaction Mechanisms

1. Sn1 Mechanism

- The intermediate carbocation is planar

- Therefore, the nucleophile OH- can attack the carbocation from either side (above or below)
with an equal chance
- This gives a pair of enantiomers in equal numbers. A racemic mixture is formed
- By measuring the original halogenoalkane and alcohol formed, it is possible to show whether
the mechanism is SN1
- Generally mechanism for tertiary halogenoalkanes is SN1
- Could also occur during the addition of HCN to carbonyl compounds
2. SN2 Mechanism

draw the mirror

image of the
reactant replacing
Br with OH-
optical activity transition state optical activity
dextrorotatory laevorotatory

- If the reactant is chiral and reaction occurs through SN2 mechanism, the opposite enantiomer
would form
- Then the optical activity of the product is different to that of reactant (product will rotate the
plane of plane polarised light in the opposite direction

- By measuring the optical activity of the original halogenoalkane and alcohol formed, we can
show whether the reaction occurs by SN2 mechanism
- Generally the main mechanism for primary halogenoalkanes is SN2.
- Both mechanisms can occur for secondary halogenoalkanes
- If the reactant is dextrorotatory, then the product will be laevorotatory or vice versa
Topic 15B Carbonyl Compounds

The carbonyl group is a carbon atom joined by a double bond to an oxygen atom. C=O
They are either aldehydes or ketones

Aldehydes

General Formulae: R-CHO

If substituents are present, the carbon of the carbonyl group is given number 1

Ketones

General Formulae: R-CO-R’

The numbering is done from the end of the longest chain that gives the lowest number for the
carbon of carbonyl group

* The C=O bond is polar because oxygen is more electronegative than carbon. The electron
density is greater near the oxygen atom than near the C atom.
* The delta negative carbon atom can be attacked by nucleophiles

Physical Properties of Carbonyl Compounds

1. Boiling Points
- Methanal is a gas at room temperature and the other carbonyl compounds are liquids
- Aldehydes and ketones contain the polar C=O group so they have permanent dipole -
permanent dipole interactions as well as London forces
- The boiling point increases with increasing molar mass because London forces increase
Alcohols Ketones Aldehydes - Aldehydes and ketones do not form
Alkanes intermolecular hydrogen bonds
because all of their H atoms are
200 attached to C atoms, not to
Boiling Temperature/ C

150 electronegative atoms like O, N or F.

100 So they do not have a hydrogen atom
50 that is sufficiently delta positive
0
-50 Alkanes: only London forces
-100
Carbonyl compounds: London forces+
-150 permanent dipole - permanent dipole
-200
0 1 2 3 4 5
Alcohols: all three intermolecular forces
Number of Carbon Atoms specially hydrogen bonding
2. Solubility in Water
- Shorter chain aldehydes and ketones are soluble in water because they can form hydrogen
bonds with water molecules

- Solubility in water decreases with increasing chain length because the London forces between
molecules predominates as the hydrocarbon part of the molecule increases

Preparation of Carbonyl Compounds (Recall AS work)

Reaction: Primary Alcohol -> Aldehyde Reaction: Secondary Alcohol -> Ketone
Reagent: Potassium Dichromate (VI) solution in dilute Reagent: Potassium Dichromate (VI) solution in
sulfuric acid dilute sulfuric acid
Conditions: Warm gently and distill out the aldehyde Conditions: Heat under reflux (to prevent the
as it forms (if not carboxylic acid would form) product escaping the system)

CH3CH2OH + [O] -> CH3CHO + H2O CH3CHOHCH3 + [O] -> CH3COCH3

ethan-1-ol ethanal propan-2-ol propanone

Qualitative Test for the Presence of Carbonyl Group

Reagent: 2,4-DNPH (2,4- dinitrophenylhydrazine) aka Brady’s reagent

Test: Add a solution of 2,4-DNPH to the test sample
Observation: Orange precipitate forms in the presence of a carbonyl group

To identify a carbonyl compound, using 2,4-DNPH

1) React the carbonyl compound with 2,4-DNPH and filter to collect the orange precipitate (2,4-
DNPH derivative)
2) Recrystallise and collect dry crystals
3) Measure the melting point and compare with the data book

Reduction Reactions of Carbonyl Compounds

Reaction: Aldehyde -> Primary Alcohol

Ketone -> Secondary Alcohol
Reducing Reagent: LiAlH4 (lithium aluminium hydride or lithium tetrahydrioaluminate (III) )
Conditions: Dry ether (ethoxyethane) as the solvent because LiAlH4 is sensitive to water so it will
react with water instead if water is present
Type of Reaction: Reduction

CH3CH2CHO + 2[H] -> CH3CH2CH2OH

CH3COCH3 + 2[H] -> CH3CHOHCH3

Oxidation Reactions of Carbonyl Compounds

* Aldehydes can be oxidized to carboxylic acid but ketones cannot be oxidized

Reagent Conditions Colour Change Notes

K2Cr2O7 in dil. H2SO4 Warm Gently Orange solution to Orange Cr2O7 2- ion reduces to green
green solution Cr 3+ ion

Fehling’s solution Warm Gently Deep blue solution Cu 2+ ions in solution reduces to Cu+,
forms brick red forming a red ppt of Cu2O
Benedict’s solution Warm Gently precipitate

Tollen’s reagent Warm Gently Colourless solution Ag+ ions in the complex is reduced to
forms silver mirror metallic silver (Ag) which forms a
coating inside the tube
* Tollen’s reagent is formed by mixing aqueous ammonia and silver nitrate [Ag(NH3)2]+

The above result as described in the table indicates the presence of an aldehyde
Negative result comfirms the absence of an aldehyde
- Thus, these oxidation reactions can be used to distinguish between aldehydes and ketones
Reaction with Iodine in Alkaline Solution/ Iodoform Reaction

This reaction gives a positive result in presence of the following group in a compound

Where R is H, alkyl (like CH3) or aryl (like C6H5) group

- Ethanal is the only aldehyde that gives a positive result (other aldehydes don’t have CH3CO
group)
- As the iodoform test is an oxidizing reaction, a secondary alcohol with a terminal methyl group
will also give a positive result

CH3CHOHR + [O] -> CH3COR

Reagent: Iodine in NaOH solution (or KOH solution)

Condition: Warm gently and allow to cool
Observation: A yellow precipitate (CHI3 - iodoform) forms. The product CHI3 is a yellow
precipitate with an antiseptic smell

CH3COR + 3I2 + 4NaOH -> CHI3 + RCOONa + 3NaI + 2H2O

Nucleophilic Addition of HCN, in the presence of KCN

Reaction: Aldehyde/ Ketone -> Hydroxy Nitriles

Reagent: HCN in presence of KCN
Conditions: Aqueous alkaline solution containing KCN (pH 8)
Mechanism: Nucleophilic Addition Reaction

HCN in KCH

CN
When naming hydroxy nitriles, the CN becomes part of the main chain (number of carbon atoms
in the chain increases by one during the reaction) and ends with - nitrile. The OH group is shown
as hydroxy-

butan-2-one 2- hydroxy - 2- methylbutanenitrile

Mechanism
Step 1) involves the nucleophilic attack by a cyanide ion on the ð+ carbon atom of the carbonyl
compound

Step 2) involves the reaction between the intermediate and a hydrogen cyanide molecule

Q. Why do we need KCN catalyst?

- Both HCN and CN- ions are essential for the reaction
- But HCN is a weak acid (low Ka) so it dissociates very slightly, producing few CN- ions
- So an alkali (pH 8) is added to produce nucleophilic CN- ions that attack the ð+ C atom
HCN <=> H+ + CN-
HCN + OH -> CN- + H2O
- KCN can also provide CN- ions that can speed up the reaction and these CN- ions are
regenerated in the mechanism

The reaction happens at about pH 8. This pH provides the catalyst which is the cyanide ion
- If the pH is too low, there are not enough CN- ions for the first step to take place
- If the pH is too high, there are not enough HCN molecules for the second step
Using Optical Activity as Evidence

- The arrangement of bonds around C=O are trigonal

planar
- Therefore, the nucleophile CN- can attack from
either side of the plane (above or below) with an
equal chance
- This produces both the enantiomers (dextrorotatory
and laevorotatory) in equal amounts so a racemic
mixture is formed
- There will be no optical activity in the product. It will
not rotate the plane of plane polarised light
Topic 15C Carboxylic Acids

General formulae: RCOOH

The suffix-oic is used in naming

give priority to C=O

ethane - 1,2 - dioic acid 5 - hydroxy - 4 - methylpentanoic acid

Physical Properties of Carboxylic Acids

1. Bonding
- Carboxylic acid group is a combination of two polarized groups, C=O and O-H
- There are three polar bonds present

delocalised
structure

- Carboxylate ion is produced during reactions, due to the loss of hydrogen atom as H+

- The charge and double bond character are evenly distributed across both oxygen atoms in the
carboylate ion
- The delocalised ion has equal C-O bond lengths
- If delocalization did not occur, the C=O bond would be shorter than C-O bond
- Carboxylate ion is much more stable because of the existence of resonance structure which
disperse its negative charge

2. Acidity
- Carboxylic acids are weak acids and only slightly dissociate in water, but they are strong
enough to displace carbon dioxide from carbonates
3. Solubility in Water
- Shorter chain carboxylic acids are soluble in water because they can form hydrogen bonds with
water molecules

- Solubility decreases with increasing chain length because the London forces between non-
polar hydrocarbon chains predominates

4. Boiling Temperature
- Carboxylic acids have high boiling points compared to other organic molecules with a similar
molar mass because they have strong hydrogen bonding between molecules
- Short chain carboxylic acids (methanoic and ehtanoic acid) form dimers through hydrogen
bonding

- Boiling temperature increases with increasing mass, because the London forces between non-
polar hydrocarbon chains increases as the carbon chain lengthens

Preparation of Carboxylic Acids

1. Oxidation of Primary Alcohols

Reaction: Primary Alcohol -> Carboxylic Acid
Reagents: K2Cr2O7 in dil. H2SO4
Conditions: Heat under reflux, use excess oxidising agent (pure product can be separated by
fractional distillation)
Observations: orange (Cr2O7 2- ion) to green (Cr 3+ ion)

CH3CH2CH2OH + 2[O] -> CH3CH2COOH + H2O

2. Oxidation of Aldehydes
Reaction: Aldehyde -> Carboxylic Acid
Reagents: K2Cr2O7 in dil. H2SO4
Conditions: Heat under reflux (pure product can be separated by fractional distillation)
Observations: orange (Cr2O7 2- ion) to green (Cr 3+ ion)

3. Hydrolysis of a Nitrile
Reaction: Nitrile -> Carboxylic Acid
Condition: Heat under reflux

Two types of reagent may be used:

a) Acidic hydrolysis
Reagent: dil. HCl or H2SO4
Equation: RCN + H+ + 2H2O -> RCOOH + NH4+
CH3CH2CN + H+ + 2H2O -> CH3CH2COOH + NH4+

b) Alkaline hydrolysis
Reagent: aqueous alkali such as aqueous NaOH solution
Equation: RCN + OH- + H2O -> RCOO- + NH3
CH3CH2CN + OH- + H2O -> CH3CH2COO- + NH3

In this case, a sodium salt is produced. In order to obtain the carboxylic acid from the salt/
carboxylate ion, a dil acid such as dil HCl or dilute H2SO4 is added to the salt
CH3CH2COO- + H+ -> CH3CH2COOH

Reactions of Carboxylic Acids

1. Reduction Reactions
Reaction: Carboxylic Acid -> Primary Alcohol
Reagent: LiAlH4
Condition: Dry ether as the solvent
Type of Reaction: Reduction
E.g Ch3CH2CH2COOH + 4[H] -> CH3CH2CH2CH2OH + H2O

2. Neutralisation Reactions
- Carboxylic acids react with alkalis, carbonates, and hydrogen carbonates to form salts
CH3COOH + NaOH -> CH3COONa + H2O
2CH3COOH + Na2CO3 -> 2CH3COONa + H2O + CO2
CH3COOH + NaHCO3 -> CH3COONa + H2O +CO2

- The effervescence caused by production of CO2 with carboxylic acids with solid Na2CO3 or
aqueous NaHCO3 can be used as a functional group test for carboxylic acids

- Carboxylic acids react with sodium to form sodium salt

2CH3COOH + 2Na -> 2CH3COONa + H2

3. Halogenation Reaction
Reaction: Carboxylic Acid -> Acyl Chlorides/ Acid Chloride
Reagent: Dry PCl5
Condition: Anhydrous conditions, room temperature (both PCl5 and acyl chloride react with
water)
Observation: Steamy fumes (of HCl gas)
e.g CH3Ch2COOH + PCl5 -> CH3CH2CClO + POCl3 + HCl (g)
* Reaction with PCl5 is used to test for the presence of OH group, which may be present in an
alcohol or a carboxylic acid (and produces steamy fumes)
- If anhydrous conditions are not used, then it is difficult to determine whether the observation of
fumes are due to the presence of OH group in water or the acid itself

4. Esterification
Reaction: Carboxylic Acid + Alcohol <=> Ester + Water
Condition: Heat under reflux and acid catalyst

- This is a slow, reversible reaction

- The oxygen atom linked to C=O in the ester comes from the alcohol
Esters have two parts to their names (eg. methyl propanoate)
- The bit ending in -yl comes from the alcohol that has formed it and is next to the single bonded
oxygen
- The bit ending in -anoate comes from the carboxylic acid and includes the C in the C=O bond
* Unlike ketones and aldehydes, carboxylic acids and their derivatives do not react with 2,4-
DNPH

Further suggested practicals:

i) solubility of a range of carboxylic acids, aldehydes and ketones
ii) preparation of carboxylic acids by the oxidation of alcohols and aldehydes
iii) reactions of carboxylic acids given in 15.12 ii, iii and iv
TOPIC 15D CARBOXYLIC ACID DERIVATIVES
Carboxylic Acid Derivatives
1. Acyl Chlorides (Acid Chloride)
Functional group: C=OCl

Their name end with -oyl chloride

Acyl chlorides are much more reactive than carboxylic acid and very susceptible to nucleophilic attack
because,
- Carbonyl carbon in acid chlorides is very δ+ as the carbon atom is joined to two highly electronegative
atoms. Because of the hydrogen of the -OH group, the carbonyl carbon of carboxylic acids is less δ+
- C-Cl bond in acid chlorides is weaker than C-OH bond in carboxylic acids
- Cl- is a better leaving group than OH- because Cl- is more stable than OH-

Reactions of Acyl Chlorides

i) Reaction with Cold Water
Reaction: Acid Chloride -> Carboxylic Acid
Reagent: Water
Condition: Room temperature
Observation: Steamy fumes of HCl
* The reaction is spontaneous at room temperature. If hot water is used, the reaction will be too fast
* Can be used as a test for the presence of acid chlorides

ii) Reaction with Alcohol

Reaction: Acid Chloride + Alcohol -> Ester
Reagent: Dry alcohol (water will react with acid chloride forming carboxylic acid)
Condition: Room temperature & anhydrous
Observations: Steamy fumes of HCl

This is a much better way to produce esters than reacting a carboxylic acid with an alcohol which is a slow,
reversible reaction
- Reaction goes to completion and its faster, does not require heat, does not require a catalyst
- However, toxic/ corrosive HCl fumes are produced

iii) Reaction with Concentrated Ammonia

Reaction: Acid Chloride + Conc. Ammonia -> Primary Amide
Reagent: Conc. Ammonia Solution
Condition: Room temperature
Observation: Misty fumes of HCl (With excess ammonia, white smoke of NH4Cl is formed)
NH3 + HCl -> NH4Cl

iv) Reaction with Amines

Reaction: Acid Chloride -> N-substituted Amide
Reagent: Amines
Condition: Room temperature
Observation: Misty fumes of HCl
HCl

HCl

* No reaction occurs with tertiary amines because there is no hydrogen

2. Esters
Physical properties of esters:
- Esters have London forces and permanent dipole-dipole interactions. They do not form intermolecular
hydrogen bonds because there are no hydrogen atoms attached to highly electronegative atoms (all Hs are
attached to C atoms)
- Esters have low melting and boiling points and are insoluble in water
- Esters have pleasant smells and are present in perfumes, food flavourings, solvents and biofuels

Reactions of Esters
i) Hydrolysis of Esters with Acids
Reactions: Ester + Water  Carboxylic Acid + Alcohol
Reagent: dil. HCl or dil. Sulfuric acid
Condition: Heat under reflux

* This reaction is reversible and does not give a good yield

* Dilute acid provides hydrogen ions, which catalyses the reaction

ii) Hydrolysis of Esters with an Alkali

Reaction: Ester + NaOH -> Sodium Carboxylate + Alcohol

* This reaction goes to completion making a carboxylate salt. This gives a higher yield of products than the
acid catalyzed hydrolysis
- The salt of the acid and the alcohol produced do not react with each other so the reaction is not reversible
- The OH- ions from the alkali are more powerful nucleophiles than water molecules (because OH- ion has a
full negative charge whereas H2O has only a partial negative charge

The salt can be converted to a carboxylic acid by adding a dilute acid

CH3COONa + HCl -> CH3COOH + NaCl

iii) Saponification
- Hydrolysis of esters with an alkali is seen in the production of soap
- Esters obtained from vegetable sources is used in soap making

3. Polyesters
- Addition polymerization
- Condensation polymerization

* Polyesters are used in soft drink bottles, food packaging and many types of clothing
* Instead of dicarboxylic acid, it is possible to use a diacid chloride which will form hazardous HCl fumes

- The artificial polyesters are not biodegradable, because microorganisms do not have enzymes that can
hydrolyse the ester linkage of these artificial fibres
- It is also possible for polyesters to form from one monomer, if that monomer contains both the functional
groups needed to react

Repeating Unit and Monomer

Further suggested practicals:

i) demonstration of the reactions of ethanoyl chloride given in 15.14 i, ii and iii
ii) the preparation of esters such as ethyl ethanoate as a solvent or a pineapple flavouring
iii) hydrolysis of an ester
Topic 15E Spectroscopy and Chromatography

Chromatography
- The stationary phase does not move during the process (solid or liquid held by a solid support)
- The mobile phase moves through or over the stationary phase at different rates, separating the mixture
(liquid or a gas)
* Those substances distributed preferentially in the mobile phase will pass through the chromatographic
system faster than those that are distributed preferentially in the stationary phase

1. Paper Chromatography

Lid – prevent the evapouration of the solvent

Container- a beaker or a rectangular box
Baseline – drawn with a pencil to prevent from dissolving in the solvent
Solvent – water or an organic solvent. Solvent level has to be below baseline to prevent the substances from
dissolving in the solvent
- A component that has a stronger affinity to the stationary phase but a weaker affinity to the mobile phase will
not travel very far up the paper, vice versa
* If the components on the chromatogram are not coloured, they can be visualized using ultraviolet radiation
(UV lamp) or by spraying with a chemical reagent that will react with the components to form a coloured
product
- Dry in a fume cupboard as the solvent is toxic
- Will get more accurate results if the solvent is allowed to rise to near the top of the plate but the Rf value can
be calculated if the solvent front does not reach the top of the table

2. Thin Layer Chromatography

- Apparatus and method are the same as in paper chromatography. Instead of paper, a sheet of glass or
plastic coated with a thin layer of a solid such as silica or alumina is used
- If using amino acid, then ninhydrin spray can be used instead of UV lamp to locate the spots
Rf Value = Distance moved by amino acid/ Distance moved by the solvent
- Each substance has its own Rf value, but some substances won’t separate because similar compounds
have similar Rf values so some spots may contain more than one compound

3. Column Chromatography
- Uses same principles as thin layer chromatography
- The stationary phase is alumina or silica packed in a tube (a burette) and soaked in a solvent (ether). The
mixture is placed on top of the stationary phase and more solvent is added on top. When the tap is opened,
the solvent drips through the tip and the components of the mixture begins to move down the tube and
separate
- When more solvent is added at the top, eventually the components leaves the column and can be collected
in a container
4. High Performance Liquid Chromatography
- HPLC is a refinement of column chromatography
- Stationary phase is solid silica and the mobile phase is a solvent

- The solvent is forced through a metal tube under high pressure, rather than being allowed to pass through
by gravity
- The particle size of the stationary phase is much smaller, which leads to better separation of the components
- The sample is injected into the column
- The components are detected after passing through the column, usually by their absorption of UV radiation
- The whole process is automated, and the results are quickly available on a computer display
- As each component reaches the detector, a signal is displayed on the computer screen. This can be used to
obtain the retention time of that component

Retention time of a component is the time taken to travel from injection to detection
- The retention time depends on factors including, the nature of the solvent, the pressure used and the
temperature inside the column
- Non-polar compounds would have stronger interactions with non-polar solvents (London forces) so they
dissolve more in them and move with the solvent. As a result non-polar compounds reach the detector sooner
and they will have a smaller retention time than polar compounds

5. Gas Chromatography
- GC is a refinement of column chromatography
- This is used for separating and analyzing compounds that can be vaporized without decomposing by giving
a measure of how much of each is present
- The mobile phase is an inert gas such as nitrogen, helium or argon which passes through a coiled tube
- Stationary phase is a high boiling point liquid adsorbed onto an inert solid coated on the inside of the tube
- After the sample is injected, the components vapourize and move through the coiled tube with the carrier
gas. They move at different speeds depending on how strongly they are attracted to the stationary phase.

- A series of peaks, one for

each component in the mixture
are recorded as they reach the
detector
- The retention time can be
used to identify components by
reference to a database of
retention times of known
substances
- Number of peaks tells us many
components are there in the
mixture
- The area under each peak will
be proportional to the
abundance of that compound
* HPLC and GC are useful in
separating components in a
mixture but not very good in
positively identifying them. Components are identified by reference to a database of retention time but it can
slightly vary as it is difficult to control the variables such as solvent, pressure, and temperature. Also some
substances may have the same retention time
* It is possible to combine HPLC and GC machines to a mass spectrometer (HPLC-MS or GC-MS) enabling
all the separated components in a mixture to be identified. This can be used for
- providing forensic evidence
- detecting banned drugs in sportsmen and racehorses
- analyzing pollutants in the environment
- detecting explosives in airport baggage
- in space probes on other planets

6. Mass Spectroscopy
- If a molecule is put through a mass spectrometer it will often break up and give a series of peaks caused by
fragments
- The peak with the largest m/z value is the molecular ion peak. This largest m/z value indicates the relative
molecular mass of the organic molecule (for butane, Mr is 58)
The formation of molecular ion peak can be written as,
M + e- -> M+ +2e-
C4H10 + e- -> C4H10+ + 2e-
- Sometimes a very small peak can be seen just right to the molecular ion peak which is referred to as M+1
peak. This is caused by presence of 13C isotope

- Peaks with smaller m/z values occur due to fragmentation

- The molecular ion fragments due to covalent bond breaking, producing a positive ion and a free radical (free
radicals are not detected)
- The tallest peak in the mass spectrum is called the base peak. This represents the ion with the highest
abundance and fragment with highest stability
CH3CH2CH2CH3 + e- -> CH3CH2CH2+ + CH3•

7. High Resolution Mass Spectrometry

- Provides a value for a relative molecular mass to four or more decimal places. Values of this degree of
precision enables a compound to be positively identified from the molecular mass alone, without the need for
any other information

8. Infrared Spectrometry
- When molecules absorb radiations, they vibrate. Vibrations can be either,
a) Stretching vibrations- where the bond length increases
b) Bending vibrations- where the bond angle increases and decreases
- Non polar molecules do not absorb IR radiation

9. Nuclear Magnetic Resonance

- NMR spectroscopy uses the low energy radio wave region of the electromagnetic spectrum
- For an atom to show up in an NMR spectrum, it must have an odd number of nucleons (protons and
neutrons)
Ex: 13C isotope have an odd number of nucleons so they are detected by NMR but not 12C isotopes as they
have an even number of nucleons
* C atoms in molecules can be detected because some of them are 13C atoms. This process is known as
carbon-13 or 13C NMR. H atoms in molecules can be detected because some of them are 1H atoms. 1H
atoms are referred as protons so this process is known as proton NMR or 1HNMR.
* As a suitable solvent CDCl3 is most commonly used as it has an even number of nucleons, meaning it does
not produce signals that interfere with the signals from H or C
* TMS is added to calibrate the spectrum (giving reference standard). TMS is non-toxic, inert and gives
spectrum that is away from others. Reference TMS is given a chemical shift 0.
a) 1HNMR Spectroscopy
- The vertical axis indicates the absorption of the radio
frequency energy
- The horizontal axis is labelled a chemical shift and has
the units ‘ppm’
- Each 1H atoms in a compound produces a signal at a
characteristic chemical shift, depending on the other
atoms it is joined to
- The chemical shift of a peak can indicate the functional
group responsible, using the diagram given in the
booklet
-The protons/ hydrogen atoms in the same chemical
environment are identical and these are often described
as equivalent protons
- The relative peak area (intensity/ integration value/
integration trace) is proportional to the number of
equivalent H atoms it represents
- Each signal in the spectrum is further split into more lines due to inequivalent Hs on neighbouring C atoms
- H protons are influenced by H protons and vice versa. H protons are not influenced by any other protons
because there are none on the adjacent carbon atom.
* If there are n number of inequivalent Hs on neighbouring C atoms, the peak for hydrogen atoms splits into
n+1 sub speaks which are sometimes referred to as multiplets (singlet, doublet, triplet, quartet, quintet)

Q. What would you predict about the appearance of the 1HNMR spectrum of methyl propane
A. – There are three different proton environments. Therefore, there will be 3 sets of peak
- Ratio of peak areas a:b:c will be 3:2:3
Proton Environment Splitting Pattern Chemical Shift
a Triplet 0 – 1.7 ppm
b Quartet 1.8 – 2.8 ppm
c Singlet 2.8 – 4.2 ppm

b) 13C NMR Spectroscopy

- Signals are produced by 13C atoms in the molecule

- The number of vertical lines/ peaks helps to identify the number of different chemical environments of carbon
atoms

- The chemical shift of the peak can be used to deduce the chemical environment