INTRODUCTION and

QUANTITATIVE
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ASPECTS OF
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 Basic principle of
Thermochem
(qualitative aspects)
 Thermal Energy
• Heat is the transfer of thermal energy
between two bodies that are at the
different temperatures.

• Heat flows from warmer objects to cooler

objects.

• Thermochemistry is the study of heat

changes in chemical reactions.

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Heat flow in thermal energy
• energy contained within a system that is responsible for its temperature.

• HEAT is the flow of thermal energy. Transformation of energy.

• it’s the energy that is associated with the random motion of atoms and
molecules

• temperature is not the measurement of the thermal energy

• it’s depends on quantity: Extensive property

HEAT & THERMAL ENERGY are different

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Thermochemistry: General Principle
• useful in predicting reactant and product quantities in a chemical
reactions.

• use to predict whether a reaction is spontaneous (natural) or non‐

spontaneous; favorable or unfavorable.

• combines the concepts of THERMODYNAMICS with the concept of energy

in the form of chemical bonds.

https://en.wikipedia.org/wiki/Thermochemistry

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 Thermochemistry
• study of the heat energy relate to
chemical reactions and/or physical
transformations.

like: phase change;

change in energy :
endothermic : absorbs heat
exothermic : releases heat
• emphases on energy changes,
particularly on the system’s energy
exchange with its surroundings.
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Heat
• Heat will flow from a hotter object to a colder object
or from higher temperature to lower temperature

Examples:
• Mix hot water with ice
Temperature of the ice rises after it melts

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 Thermochemistry
Process of heat flow:
change of energy:
• Endothermic process/energy/reaction:
* heat from the surrounding;
* temperature of the surrounding
decreases.
** system becomes hotter

• Exothermic process/energy/reaction:
* release heat to the surrounding;
* temperature of the surrounding
increases.
** system becomes colder 8
Principles of Heat Flow: System and Surrounding
• The system: that part of the universe on which attention is focused

• The surroundings: the rest of the universe

• Practically speaking, it is possible to consider only the surroundings that

directly contact the system

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Principles of Heat Flow: System and
Surrounding
• Thermodynamic System/System
The substance under study in which
a change occurs is called the
thermodynamic system

• Thermodynamic
Surroundings/Surroundings
Everything else in the vicinity is
called the thermodynamic
surroundings (or just the
surroundings).

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 Chemical Reactions:
• System: reactants and products

• Surroundings:
are the vessel (beaker, test
tube, flask) in which the
reaction takes place plus the
air or other material in thermal
contact with the reaction system
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Systems and Surroundings

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 THREE TYPES OF SYSTEM
1. Open System: e.g. water in an open container. Can exchange
mass and heat with surroundings(in the form of heat).

2. Closed System: e.g. water in a closed containers. Only transfer

of energy, not mass.

3. Isolated System: e.g. water in an insulated container. No

transfer of mass or energy.

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 EXOTHERMIC process/reactions: ENERGY/HEAT IS ENDOTHERMIC process/reaction: ENERGY/HEAT IS
RELEASED FROM SYSTEM TO THE SURROUNDING ABSORBED FROM SURROUNDING TO THE SYSTEM
Making ice cubes (freezing or solidification) Melting ice cubes
Formation of snow in clouds Conversion of frost to water vapor
Condensation of rain from water vapor (condensation) Evaporation of water (evaporation)
A candle flame (combustion reaction) Forming a cation from an atom in the gas phase
Mixing sodium sulfite and bleach Baking bread
Rusting iron (corrosion) Cooking an egg (cooking foods)
Burning sugar Producing sugar by photosynthesis
Forming ion pairs Separating ion pairs
Combining atoms to make a molecule in the gas phase Splitting a gas molecule apart
Mixing water and acids or bases (strong or weak) Mixing water and ammonium nitrate/ammonium chloride
Mixing water from anhydrous salt Making an anhydrous salt from a hydrate
Crystallizing liquid salts (ex.: sodium acetate in chemical Melting solid salts
handwarmers)
Nuclear fission Reaction of Ba(OH)2•8H2O crystal with dry NH4Cl
Mixing water with CaCl 2 Mixing water with KCl
Hot packs Sublimation process
Neutralization reaction Fusion of solid
Fireworks Ice packs
Dissolving sodium chloride in water Boiling
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https://www.thoughtco.com/endothermic‐reaction‐examples‐608179
 Exercises:
Classify the following as an endothermic or exothermic reaction:
1. freezing water
2. the reaction inside an ice pack
3. burning wood
4. combustion of Mg in dry ice
5. melting ice
6. making popcorn in a microwave
7. a burning match
8. boiling water
9. burning rocket fuel
10. the reaction inside a heat pack
•

https://quizlet.com/78153966/outcome‐49‐flash‐cards/
•
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•
 Direction and Sign of Heat Flow
• Heat is given the symbol: q or Q

• q is positive when heat flows into the system from the

surroundings (endothermic process)
Endothermic processes have positive q
H2O (s)  H2O (ℓ) + heat q>0

• q is negative when heat flows from the system into the

surroundings (exothermic process)
Exothermic processes have negative q
CH4 (g) + 2O2 (g) + heat  CO2 (g) + 2H2O (ℓ) q<0

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Magnitude of Heat Flow
• In any process:
direction of heat flow and in its magnitude
• q, Q ‐‐‐ is expressed in joules, J (or kilojoules, kJ)
[James Joule (1818‐1889); ] ….. calorimetry
• Alternate unit: calorie
• 1 calorie = 4.184 J
• 1 kilocalorie = 4.184 kJ
• Nutritional calories are kcal

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 QUANTITATIVE
ASPECTS OF HEAT
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Measurement of Heat Flow: Calorimetry
Calorimetry
• Science of measuring heat based on the change in temperature of an
observed body when it releases and /or absorbs heat

• The temperature change is based on the heat capacity of the body.

(The higher the heat capacity the higher its boiling point)

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Measurement of Heat Flow: Calorimetry
• A calorimeter is a device used to measure the heat flow of a reaction

• The walls of the calorimeter are insulated to block heat flow between the
reaction and the surroundings

• The heat flow for the system is equal in magnitude and opposite in sign from
the heat flow of the calorimeter

qreaction = ‐ qcalorimeter

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Types of calorimeter
• Coffee – cup calorimeter

• Bomb calorimeter

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 Coffee‐cup Calorimeter

https://ch301.cm.utexas.edu/section2.php?target=thermo/thermochemistry/coffee‐cup‐calorim.html 22
Coffee‐cup Calorimeter: Characteristics:
• is a constant pressure calorimeter (isobaric).

• it involves with little or no volume change.

• uses simple styrofoam cup.

styrofoam cup makes for a good adiabatic wall and

helps keep all the heat released or absorbed by the reaction

inside the cup for measurement.

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Coffee‐cup Calorimeter principle:
• heat of calorimeter, q cal (or called heat of reaction, q reaction) can
be determined from the mass of the substance multiplied by the
specific heat capacity of the substance, Cp and change of
temperature, ΔT of the substance.

Heat of calorimeter q cal is equal to the heat of the system, – qp system at constant
pressure,

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 The Coffee‐cup Calorimetry Equation:
Mathematical equation:
q = m x Cp x Δt
where: (for any substance)
q = heat of reaction or heat flow or heat of calorimeter in J or kJ;
m = mass of the substance in g;
Cp = specific heat capacity of the substance in J/g•0C , J/g•K or kJ/g•0C, kJ/g•K
ΔT = temperature change in 0 C or K of the substance

NOTE:
• Many tables will list specific heat capacities using °C instead of K.
• These two units are equivalent because we are using ΔT and not plain T.
• A change in Kelvin of 10 is exactly a change of 10 in °C as well.
• Don't try to change Celsius to Kelvin and vice versa here. 25
 The Coffee‐cup Calorimetry Equation:
Mathematical equation:

q = m x Cp x Δt

Ex.: if the substance is water

q cal = q reaction = m waterCp,waterΔT water = − qp, system
– qp,system = heat of the system at constant pressure (heat flows from the system to
the surroundings)

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The Coffee‐cup Calorimetry Equation: Heat, q
Heat , q = change in enthalpy, ΔH
(enthalpy = chemical energy involve in the heat flow of chemical
reaction between the reactants and products))
• q is positive when heat flows from the surroundings into the system ,
ΔH is positive…
Endothermic processes: melting of ice
H2O (s) +heat  H2O (ℓ) ΔH > 0
• q is negative when heat flows from the system into the surroundings,
ΔH is negative
Exothermic processes: combustion of fuel
CH 4 (g) + 2O 2 (g)  CO 2 (g) + 2H2O (ℓ) + heat ΔH < 0 27
 The Coffee‐cup Calorimetry Equation: mass, g
Mass of the substance: mass
is related to the volume and
• Vol. = ‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐
density of the substance.

Unit: grams, g
• mass = vol. x 
Using the density,  of the substance:
mass
 = ‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐
volume
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 The Coffee‐cup Calorimetry Equation: Specific
Heat Capacity or heat capacity, Cp
Specific heat capacity, Cp or C,

• the quantity of heat needed to raise the temperature of one gram of a

substance by 1 K or 1 0 C

• unit is J/g•0C ; J/g•K ; kJ/g•0C ; kJ/g•K

• depends on the identity and phase of the substance: solid, liquid or gas (vapor)

• The specific heat of a substance, like the density, melting point, boiling point, is an intensive
property that can be used to identify a substance or determine its purity, it is an intensive
property. 29
30
The Coffee‐cup Calorimetry Equation:
express in Molar Heat Capacity, Cm
Cp of water = 4.184 J/g 0C or 4.184 J/g K
Conversion of Cp to Cm
To convert to molar heat capacity, Cm: using: molar mass
convert to molar heat capacity, Cm
Cm = Cp x molar mass
molar mass of water: 18 g/mole
Cm = 4.184 J/g 0C x 18 g/mole = 75.31 J/mol 0C or 75.31 J/mol K

NOTE:
• Many tables will list specific heat capacities using °C instead of K.
• These two units are equivalent because we are using ΔT and not plain T.
• A change in Kelvin of 10 is exactly a change of 10 in °C as well.
• Don't try to change Celsius to Kelvin and vice versa here. 31
The Coffee‐cup Calorimetry Equation:
express in Molar Heat Capacity, Cm
Conversion of Cm to Cp
Cm of water = 75.31 J/mol 0C
To convert to specific heat capacity, Cp: using: molar mass
convert to specific heat capacity, Cp
Cp = Cm  molar mass
molar mass of water: 18 g/mole
Cm = 75.31 J/mol 0C  18 g/mole = 4.184 J/g 0C or 4.184 J/g K

NOTE:
• Many tables will list specific heat capacities using °C instead of K.
• These two units are equivalent because we are using ΔT and not plain T.
• A change in Kelvin of 10 is exactly a change of 10 in °C as well.
• Don't try to change Celsius to Kelvin and vice versa here. 32
The Coffee‐cup Calorimetry Equation: temperature
change, ΔT in 0 C or K of the substance
• ΔT is the change in temperature of the substance/s when heat
exchange will occur.

• Initial temperature, t1 and final temperature, t2

• ΔT = (t2 – t1)

Q, q = m Cp Δt
Energy Transferred as Heat ( 2 systems)
Determining the specific heat capacity of one of the substance or final
temperature of the reaction, etc….. between two substances example:
water and metal.
Assumption:
1. System: water and heated metal
2. Surroundings: Apparatus used like coffee‐cup and the environment
3. Energy is transferred only as heat within the system.
4. Water and metal have the same final temperature. (thermal
equilibrium)

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 Energy Transferred as Heat (2 system)
Determining the specific heat capacity of a substance, between water and metal
Assumption:
5. q of heated metal, qm …. has a negative value (temp. decreases).. Release heat to the water
6. q of water, qw …. has a positive value (temp. increase) … absorb heat from the hot metal
7. qm and qw are numerically equal but are opposite in sign
8. Using : Law of Conservation of Energy:
In an isolated system the sum of energy changes within the system
is equal to zero. (If energy is transferred only as heat)
mathematical equation:
q1 + q2 + q3 + …. = 0 Hot metal
for water and metal qm + qw = 0
qw = – qm

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 The Coffee‐cup Calorimetry Equation: summary
For 2 systems:
• q = m x Cp x Δt heat absorbed = – heat released
endothermic = – exothermic
• q = m x Cp (t2 – t1) q endo = – q exo

• m= q  Cp (t2 – t1) water, w and heated metal, hm:

• qw = – qm
• Cp = q  m (t2 – t1)
• [m x Cp x Δt]w = [– m x Cp x Δt]hm
• Δt = q  m x Cp
• [m x Cp x (t2 – t1) ]w = [– m x Cp x (t2 – t1) ]hm
• (t2 – t1) = q  m x Cp
t2w = t2hm (thermal equilibrium: final temperature for
both water and hot metal are the same)
 Problem Solving
show complete solution

(meaning... Show the formula use, substitution of values into

the formula with complete units, complete conversion,
cancellation of units)
Sample problem:
1. A piece of zinc weighing 35.8 g was heated from 20.00°C to 28.00°C. How much heat
was required? The specific heat of zinc is 0.388 J/g°C.

Given: mass of Zn metal = 35.8 g t2 = 28.00°C

t1 = 20.00°C Cp of Zn metal = 0.388 J/g°C

Rqd: heat, q

Solution: q = m x Cp x Δt
q = m x Cp (t2 – t1)

substituting the values :

q = 35.8 g x 0.388 J/g°C (28.00°C ‐ 20.00°C)

q = 111 J
 Sample problem:
2. The temperature of a 15‐g sample of lead metal increases from 22 °C to 37 °C
upon the addition of 29.0 J of heat. The specific heat capacity of the lead is
__________ J/g‐K.
Solution:
3. A sample of aluminum metal absorbs 9.86 J of heat, upon which the
temperature of the sample increases from 23.2 °C to 30.5 °C. Since the specific
heat capacity of aluminum is 0.90 J/g‐K, the mass of the sample is __________ g.

4. If 50.0 g of benzene, C6H6, at 25.00C absorbs 2.71 kJ of energy in the form of

heat, what is the final temperature of the benzene? The specific heat of benzene is
1.72 J/g.0C.

39
 Sample Problem:
5. How much heat in kJ is needed to warm 1 cup of water (about 1 cup = 250 mL ) from 22 0 C to 98 0 C. (molar heat capacity of water,
Cm of water is 75.312 J/mol 0C and density of water is 1.00 g/mL).

• Given: volume of water = 1 cup (1 cup = 250 mL); Cm = 75.312 J/mol; t1 = 22 0 C ; t2 = 98 0 C;  = 1.00 g/mL
• Rqd.: heat in kJ , qw
• Solution: q = mxCpxΔt mass in g, Cp in J/g0C , temperature in 0C
note from the given values that volume and molar heat capacity is given; so it cannot be use in the formula to
determine the heat of water.
convert first the volume to mass and the molar heat capacity to specific heat capacity of water
to convert volume of water to mass of water use( then cancel units) : conversion factor den use density of the water
mass of water = 1 cup x 250 mL/1 cup x 1.00 g/1 mL = 250 g
to convert molar heat capacity, Cm to specific heat capacity, Cp use the molar mass of water:
solving for the molar mass of H2O = (2 x 1 g/mol ) + (1 x 16 g/mol) = 18 g/mol
Cp = 75.312 J/mol 0C x 1 mol/18g = 4.184 J/g 0C
substitute the converted values to the formula:
q = mxCpxΔt = m x Cp (t2 – t1) = 250 g x 4.184 J/g 0C (98 0 C ‐ 22 0 C)
q = 79,496 J
convert J to kJ : 1 kJ = 1000 J
q = 79,496 J x 1kJ/1000 J
40
q = 79.496 kJ
 Sample problem:
6. A 55.0 g piece of metal is heated in boiling water to 99.8 0 C and then dropped into cool water in an isolated
beaker. The beaker contains 225.0 g of water and its temperature (before the metal was dropped in) was 21.0
0 C . The final temperature of the metal and water is 23.1 0 C( thermal equilibrium). What is the specific heat
capacity of the metal? Cp of water is 4.184 J/g0C

• Given: mass of metal = 55.0 g ; t1m = 99.8 0 C; Cpw = 4.184 J/g0C

mass of water = 225.0 g; t1w = 21.0 0 C; t2m = t2w = 23.1 0 C
• Rgd.: specific heat capacity of metal, Cpm
• Solution: for two systems: the metal release heat to the water and the water absorbs heat from the metal
its mathematical equation is:
qw = – qm
(mxCpxΔt)w = (–mxCp xΔt)m
Cpm = (mxCpxΔt)w /(–mxΔt)m
Substituting the given values and cancellation of units and simplifying:
Cpm = [mxCp(t2‐tt1)]w /[–m(t2‐tt1)]m
Cpm = [225.0 g x 4.184J/g0C (23.1 0 C ‐ 21.0 0 C )] /[–55.0 g (23.1 0 C ‐ 99.8 0 C )]
Cpm = 0.469 J/g0C
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Sample problem:
7. A 88.5 –g piece of iron whose temperature is 78.8 0 C is place in a
beaker containing 244 g of water at 18.8 0 C. When thermal equilibrium
is reached, what is the final temperature? (Assume no energy is lost to
warm the beaker and its surroundings). Cp of water is 4.184 J/g0C and
the Cp of iron is 0.446 J/g 0C.

8. When 225 mL of water at 25 0 C are mixed with 85.0 mL of water

at 85 0 C, what is the final temperature ? (Assume that no heat is lost
to the surroundings. (density of water is 1.00 g/mL)

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Sample problem:
9. Compare the amount of heat given off by 1.40 mole of liquid water
when it cools from 100.0 0 C to 30.0 0 C to that given off when 1.40 mol
of steam cools from 200.0 0 C to 110. 0 C (Cp of H2O (l) = 4.184 J/g. 0 C;
Cp of H2O (g) = 1.87 J/g. 0 C). Explain your coparison.

10. 30.0 g H2O at an unknown temperature is mixed with 27.0 g of

water at 15.80C in a coffee‐cup calorimeter. If the final temperature of
the mixture is 29.10C, what is the initial temperature of the water?

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Sample Problem
11. What is the enthalpy change/heat (in kJ) of a chemical reaction
that raises the temperature of 250.0 ml of solution having a density of
1.25 g/ml by 7.80°C? (The specific heat of the solution is 3.74
joules/gram‐K.)

12. How much energy must be transferred to raise the temperature of

a cup of coffee (250 mL) from 20.4 0 C to 95.6 0 C. Assume that the
water and coffee have the same density (1.00 g/mL) and specific heat
capacity is 4.19 J/g. 0 C.
44
 Sample problems:
13. If the same amount of energy in the form of heat is added to 5.00 g samples of
each of the metals below, which metal will undergo the largest temperature
change?
Metal Specific Heat (J/g0C)
Ag 0.235
Al 0.897
Cu 0.385
Fe 0.449
Hg 0.140

45
Sample problem:
14. When a student mixes 50.0 mL of 0.1 M HCl and 50.0 mL of 0. M
NaOH in a coffee‐cup calorimeter, the temperature of the resultant
solution increases from 21.0 0 C to 27.5 0 C. Calculate for the enthalpy
change for the reaction in kJ, assuming that the calorimeter loses only a
negligible quantity of heat, that the total volume of the solution is 100.0
mL, that its density is 1.0 g/mL and that its specific heat is 4.18 J/g 0 C

46
Sample problem:
15. Sodium chloride is added in cooking to enhance the flavor of food.
When 10.0 g of NaCl is dissolved in 200.0 mL of water at 25.0 0 C I a
coffee‐cup calorimeter. 669 J of heat are absorbed. (You can make the
following assumptions about the solution. Volume = 200.0 mL, density
is 1.0 g/mL, specific heat capacity = 4.18 J/g 0 C.
a) Is the solution process endothermic?
b) What is q H2O ?
c) What is the final temperature of the solution?

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 Bomb Calorimeter
• Heat of reactions for
both solutions and gases

• High pressure

• Combustion reaction occur

48
 Bomb Calorimetry (Constant Volume Calorimetry)

• Heat of reactions for both solutions and gases

• High pressure
• Combustion reaction occur
Bomb Calorimeter: principle
• is a constant volume calorimeter (constant volume is isochoric).

• the heat of the bomb calorimeter, qcal is equivalent to the change in internal
energy and change of enthalpy: qcal = ΔH= ΔU

• qcal. is determined from the heat capacity of the calorimeter, Ccal. , and
change in temperature, ΔT

• Heat capacity of the calorimeter C cal is used to find heat of the system at
constant volume q v, system:

50
Bomb Calorimetry Equation:
Its mathematical expression:
q cal = C calΔT = − q v, system
where:
qcal = heat of calorimeter in J or kJ;
C cal= heat capacity in J/ 0 C or kJ/ 0 C ; J/ K or kJ/K;
ΔT = change in temperature in 0 C or K
− q v, system = heat of the system at constant volume
it has an opposite sign (exothermic)

51
 Bomb Calorimetry Equation:
Mathematical equation for the heat of
reaction,
q reaction.:
q reaction = – q cal
= – Ccal ΔT

52
 Bomb Calorimetry Equation:
Heat of reaction involved the presence of water:
• water is an important component in the bomb calorimeter
• heat produced by the reaction is absorbed by the water and
calorimeter
Mathematical Equation:

q reaction = – (q cal + q water)

where: qcal = – C calΔT
and: q water = mwaterCp,waterΔT
q reaction = – ( C calΔT + mwaterCp,waterΔT)

53
 Bomb Calorimetry Equation:
calculating heat, q …. involves stoichiometry
Recall : unit of q is in J or kJ

• If heat, q is required in J/g or kJ/g:

convert: divide it with given mass
q = J/given mass or q = kJ/given mass

• If heat, q is required in kJ/mole:

convert: divide it with the no. of moles
no. of moles = mass / molar mass
q = J/no. of moles
54
Sample problem:
1. A chemical reaction in a bomb calorimeter evolves 3.15 kJ of heat. If
the temperature of the calorimeter is raised from 19.19°C to 22.03°C,
what is the heat capacity of the calorimeter?
• Given: qcal = ‐ 3.15 kJ; t1 = 19.19 0 C; t 2 = 22.03 0 C
• Rqd: Cp of calorimeter
• Solution: qcal = ‐ qevolve = ‐ Ccal Δt
Ccal = ‐q/‐ (t2‐t1)
= ‐3.15kJ/‐(22.03 0 C – 19.19 0 C)
Ccal = 1.11 kJ/°C
 Sample problem:
2. Hydrogen chloride, HCl (g) use in etching semiconductors. It can be prepared by reacting hydrogen and chlorine gas:
H 2 (g) + Cl 2 (g)  2 HCl (g) It is found that when 1.00 g of H 2 (g) is made to react completely with Cl 2(g) in a bomb calorimeter
with a heat capacity, C cal. of 5.15 kJ/0 C, the temperature in the bomb rises from 20.00 0 C to 29.82 0 C. The calorimeter can hold
1.000 kg of water. How much heat is evolved by the reaction?
• Given: mass of H2 (g) = 1.00 g ; mass of water 1.00 kg= 1000 g (convert to g) ; Ccal. = 5.15 kJ/0C ; t 2 = 29.82 0C ; t 1 = 20.00 o C
• Rgd: q of reaction, q reaction
• Solution: heat evolved in the reaction that involved water is:
q reaction = – (q cal + q water)
where: qcal = C calΔT
q water = mwaterCp,waterΔT
solve q of water :
q water = m x Cp x Δt = 1000 g x 4.184 J/g0C (29.82 0C– 20.00 0C) = 41,086.88 J
convert to J to kJ q water = 41,086.88 J x 1 kJ/1000 J = 41.09 kJ (for consistency of unit with Cp of the bomb calorimeter)
solve for q of cal. :
q cal. = Ccal x ΔT = 5.15 kJ/0 C (29.82 0C– 20.00 0C) = 50.57 kJ
substitute to the equation of q of reaction:
q reaction = – (q cal + q water) = – (50.57 kJ + 41.09 kJ)
56
q reaction = – 91.66 kJ
 Sample problem:
3. Hydrazine, N2H4 (l), and its derivatives are widely used as rocket fuels. The combustion of hydrazine with oxygen
produces N2(g) and H2O (gas) : N2H4 (l) + O 2  N2(g) + H2O (gas)
When 1.00 g of hydrazine is burned in a bomb calorimeter, the temperature of the calorimeter increases by 3.51 0 C.
If the calorimeter has a heat capacity of 5.510 kJ/ 0 C, what is the heat of reaction?, what is the heat evolved for the
combustion of one mole of N2H4 (l) in kJ/mol.
• Given: mass of N2H4 (l) = 1.00 g ; ΔT = 3.51 0 C ; Ccal. = 5.510 kJ/0C.
• Rqd: A) q rxn B) heat evolved of 1 mol of N2H4 (l) in kJ/mol containing 1 g of N2H4 (l)
• Solution: A) q rxn = – q cal = – Ccal x ΔT = – 5.510 kJ/ 0 C (3.51 0 C) = – 19.3 kJ
B) q evolved = ‐ q rxn
for 1 mole of N2H4 (l) containing 1 g of N2H4 (l)
q evolved = q rxn/no. of moles
* solve for the molar mass of N2H4 (l) = 2x14 g/mol + 4x1 g/mol = 32.0 g/mol
* solve for no. of moles = 1 g / 32.0 g/mole = 0.03125 moles
substituting the values:
q evolved = – (19.3 kJ /0.03125
q evolved = – 617.60 kJ/mole
57
 Sample problem:
4. The combustion of benzoic acid, C7H6O2, can be used to determine the heat capacity of a bomb
calorimeter. The heat evolved per mole of benzoic acid combusted is 3.09 x 103 kJ. If the combustion of 1.00 g
of benzoic acid increases the temperature of a calorimeter by 7.530C. What is the heat capacity of the
calorimeter?
• Given: mass of C7H6O2 = 1.00 g ; qevolve = ‐ 3.09 x 10 3 kJ/mol; Δt = 7.530C
• Rqd: Cc al.
• Solution: q cal = ‐ q evolve = ‐ Ccal x Δt
‐ Ccal = ‐ q evolve / Δt
q must be in kJ ….. but the given q is 3.09 x 10 3 kJ/mol
* convert q in kJ/mol to q in kJ using the given mass and the molar mass of C7H6O2
q in kJ = q in kJ/mol x no. of moles
solve for the molar mass of C7H6O2 = 7x 12 g/mol + 6 x 1 g/mol + 2 x 16 g/mol = 122 g/mol
no. of moles = mass/molar mass = 1 g / 122 g/mole = 8.197 x 10 – 3 moles
q evolve = ‐ 3.09 x 10 3 kJ/mol x 8.197 x 10 – 3 moles = – 25.33 kJ
substitute the value of q in kJ:
‐ Ccal = – q evolve / Δt = ‐ 25.33 kJ / 7.530C
‐ Ccal = – 3.364 kJ/oC
Ccal = – 3.364 kJ/oC 58
Sample problem:
5. A 0.5865‐g of lactic acid, CH3H5O3 , is burned in a bomb calorimeter,
whose heat capacity is 4.812 kJ . The temperature increases from
23.10 0 C to 24.95 0 C. Calculate the heat of combustion of lactic acid
per gram and per mole.

59
Sample Problem:
6. The combustion of methylhydrazine, CH6N2; a rocket fuel, produces
N2(g), CO2(g) and H2O(l):
2 CH6N2(g) + 5 O2(g)  2 N2(g) + 2 CO2(g) + 2 H2O(l)
When 4.0 g of methylhydrazine is combusted in a bomb calorimeter,
the temperature of the calorimeter increases from 25.0 0 C to 39.50 0 C.
In a separate experiment the heat capacity of the calorimeter is
measured to be 7.794 kJ/ 0C. Calculate the heat of reaction for the
combustion of a mole of CH6N2 .

60
Sample problem:
7. Acetylene, C2H2, is a gas used in welding. The molar enthalpy of
combustion for acetylene is –2599 kJ. A mass of 0.338 g C2H2(g) is
combusted in a bomb calorimeter. If the heat capacity of the
calorimeter is 5.54 kJ/0C, what is the temperature increase of the bomb
calorimeter?

61
Sample problem:
8. Isooctane is a primary component of gasoline and gives gasoline its
octane rating. Burning 1.00 mL of isooctane (d = 0.688g/mL) releases
33.0 kJ of heat. When 10.0 mL of isooctane is burned in a bomb
calorimeter, the temperature in the bomb increases from 23.20C to
66.50C. What is the heat capacity of the bomb calorimeter?

62
 Thermochemical equation: principle
• chemical equation that includes the amount of energy, in the form of heat that is
transferred in the reaction.
Heat , q = change in enthalpy, ΔH/mol
(enthalpy = chemical energy involve in the heat flow of chemical
reaction between the reactants and products per mole)

• Chemical equation that shows the enthalpy relation between products and
reactants

• Balanced chemical equation: coefficient represents the number of moles

H2(g) + Cl2 (g)  2 HCl(g) ΔH = – 185 kJ/mole
1 mol 1 mol 2 mol
63
 Thermochemical equation: principle
• Involves stoichiometry: involves molar mass, mass and coefficient from the balance equation (no. of
moles)
H2(g) + Cl2 (g)  2 HCl(g)
1 mol 1 mol 2 mol
• Heat involves in the reactant/s and product/s

• Physical state of the substances in the chemical equation must be specified

• Values of enthalpy in the chemical reaction/equation must be of the same temperature

• Value of ΔH in forward reaction is equal to the backward reaction but opposite in sign.
H2(g) + Cl2 (g)  2 HCl(g) ΔH = – 185 kJ/mole
ΔH is for the forward reaction reactant towards the product
ΔH is for the backward reaction product to the reactant ……. ΔH = + 185 kJ/mole
64
Thermochemical equation: principle
• Heat is considered as a product or reactant in the balanced equation.

• Endothermic processes have positive q

H2O (s) + heat  H2O (ℓ) q > 0, ΔH > 0

• Exothermic processes have negative q

CH 4 (g) + 2O 2 (g)  CO 2 (g) + 2H2O (ℓ) + heat q < 0, ΔH < 0

65
Thermochemical equation: principle
Heat q, = heat of reaction, q reaction = change of enthalpy, ΔH

Change of enthalpy , ΔH can be:

• Heat of reaction/heat of combustion

• Heat of formation
• Heat of evaporation
• Heat of condensation
• Bonding Energy

66
Thermochemical equation: principle
Illustration: (from stoichiometry)
H2(g) + Cl2 (g)  2 HCl(g) ΔH = – 185 kJ/mol
1 mol 1 mol 2 mol
This leads to conversion factors: (from the balance equation)
like for example:
– 185 kJ/ 1 mole of H 2(g) = – 185 kJ/mole of H 2(g)

– 185 kJ/ 1 mol of Cl2(g) = – 185 kJ/mol of Cl2(g)

– 185 kJ/ 2 mol of HCl = – 92.5 kJ/mole of HCl

CONVERT THE HEAT OF REACTION FROM kJ/mole to kJ or J/mole to J

using this conversion: ΔH rxn. = ΔH x no. of moles

67
 Sample problem:
1. Calculate the heat of reaction in kJ of 1 gram of ammonium nitrate from the given
equation: NH4NO3 (s)  NH4+ (aq) + NO3‐ (aq) ΔH = + 351 J/mol

• Given : ΔH = + 351 J/mol; 1 g ammonium nitrate

• Rqd: ΔH rxn. in kJ
• Solution:
ΔH rxn. = ΔH x no. of moles
Solve : molar mass of NH4NO3 = 14 g/mole x 2 + 1 g/mole x4 + 16 g/mole x 3
= 80 g/mol
solve for the no. of moles = mass/molar mass = 1 g/80 g/mole =0.125 moles
ΔHrxn. = 351 J/mole NH4NO3 x 0.0125 moles
= 4.388 J
Convert to kJ :
ΔHrxn. = 4.388 J x 1kJ/1000 J
ΔHrxn. = 4.388 x 10 – 3 kJ
 Sample problem:
2. Calculate the heat of reaction/enthalpy in kJ of 5 gram of ammonium nitrate from
the given equation: NH4NO3 (s)  NH4+ (aq) + NO3‐ (aq) ΔH = + 351 J/mol
• Given: ΔH = + 351 J/mol; 5 g ammonium nitrate
• Rqd.: ΔHrxn in kJ
• Solution:
ΔHrxn = ΔH x no. of moles
Solve : molar mass of NH4NO3 = 14 g/mol x 2 + 1 g/mol x4 + 16 g/mol x 3
= 80 g/mol
no. of moles = mass/molar mass = 5 g/80 g/mole = 0.0625 moles
substituting the values:
ΔH = 351 J/mole NH4NO3 x 0.0625 moles
= 21.938 J
Convert to kJ :
ΔH = 21.938 J x 1kJ/1000 J
ΔH = 2.194 x 10 – 2 kJ
Sample problem:
3. Calculate the amount of heat produced in kJ from the combustion of 10.0 g of C2H6 which burns in
oxygen.
2 C2H6(g) + 7 O2 (g)  4 CO2 (g) + 6 H2O (g) ΔH = – 3138 kJ/mole

• Given: ΔH = – 3138 kJ/mole; mass = 10.0 g C2H6

• Rqd: ΔHrxn in kJ
• Solution:
ΔHrxn = ΔH x no. of moles
But since the coefficient in C2H6 (g) is 2 (refer from the balance equation) : divide first
the given ΔH into two. So, the ΔH per mole of C2H6(g) is:
ΔH = ΔH /no. of moles = – 3138 kJ/ 2 mol = – 1569 kJ/mol
solving for molar mass of C2H6 = 12 g/mole x2 + 1 g/mol x 6 = 30 g/mole
solve for the no. of moles = maas/molar mass = 10.0 g/30 g/mol = 0.3333 moles
substitute the values:
ΔHrxn = – 1569 kJ/mol x 0.3333 mole
ΔHrxn = – 523 kJ
Sample problem:
4. The Bunsen burner in your labs are fueled by natural gas, which is
mostly methane, CH4. The thermochemical equations for the
combustion of methane (burning in oxygen) is:
CH4(g) + 2 O2(g)  CO2(g) + 2 H2O (g) ΔH = – 890.3 kJ
Calculate ΔH when:
A) 5.00 g CH4 react with an excess oxygen.
B) 2 L of O2 at 49 0 C and 782 mm Hg react with an excess of methane.

71
Sample problem:
5. Calculate the amount of heat produced in kJ from the combustion of
10.0 g of C2H6 which burns in oxygen and produces carbon dioxide and
water and evolves –3135 kJ/mole of heat.

Write the chemical equation.

Molar mass of C 2H 6
Solve the ΔH using the balance equation

72
Sample problem:
6. Iron oxide reacts with aluminum in an exothermic reaction.
Fe2O3(s) + 2Al(s)  2Fe(s) + Al2O3(s) The reaction of 5.00 g Fe2O3 with
excess Al evolves 26.6 kJ of energy in the form of heat. Calculate the
enthalpy change per mole of Fe2O3 reacted.

73
Sample problem:
7. Methane, CH4, reacts with oxygen to produce carbon dioxide, water,
and heat.
CH4(g) + 2O2(g)  CO2(g) + 2H2O(l) ΔH = – 890.3 kJ
What is the value of ΔH if 5.00 g of CH 4 is combusted?

74
Heat of formation, ΔH0 f (standard enthalpy of
formation)
• Enthalpy change/heat of reaction , for the formation of 1 mole of the
compound is formed at a constant pressure of 1 atm and a fixed
temperature (25 0 C) from the elements in their standard states at
constant pressure.

• Heat of formation, ΔH0 f values of different substances is given in a

table.

Standard states is the most stable form of an elements

75
Heat of formation, ΔH0 f (standard enthalpy of formation)
Stable form of an elements: (at standard states)

• FREE ATOM : all elements in the periodic table

Example: Fe , K, Na, Mn, Zn, C

• DIATOMIC MOLECULE = like : H 2(g) , Cl 2(g) , F 2(g) , I 2(s) , Br 2(l) ,

O 2(g) , N 2(g)
(take note of the physical state of the substances)
Value of enthalpy change, ΔH = 0 (of the above substances)
Except for:
Br2(g) = +29.6 kJ/mole
76
Table 8.3
Table 8.3,
(Cont’d)
 Heat of formation, ΔH0 f ….. General rule:
• Used to determine the standard enthalpy change, ΔH0 , ΔH0 std. or enthalpy of
reaction or heat of reaction, ΔH0r for a given thermochemical equation.
• Used to determine the heat of formation, ΔH0 f of one of the substances in a
given chemical equation.
• Physical state of the substances in the chemical equation must be specified
• Heat of formation, ΔH0 f value of different compounds and ions in aqueous
solution is listed in a Standard Enthalpies of Formation at 25 0 C Table in
kJ/mole
• Heat of formation, ΔH0 f value of the substances in their standard state is
equal to zero, 0 and can be omitted.
• Chemical equation must be balance. Coefficient of products and reactants in
the thermochemical equation must be taken into account.
79
 Heat of formation, ΔH0 f ….. General rule:

• Used to determine the standard enthalpy change, ΔH0 , ΔH0 std. or

enthalpy of reaction or heat of reaction, ΔH0r for a given
thermochemical equation. Its equation is :
ΔH0r =  ΔH0f (product/s) –  ΔH0f (reactant/s)
• Physical state of the substances in the chemical equation must be
specified
example: CH4(g) + 2 O2(g)  CO2(g) + 2 H2O (g)
ΔH0r =  ΔH0f (product/s) –  ΔH0f (reactant/s)
ΔH0r = ΔH0 f CO2(g) + ΔH0 f H2O (g) – ΔH0 fCH4(g) + ΔH0 f O2(g)
80
 Heat of formation, ΔH0 f ….. General rule:
• Heat of formation, ΔH0 f value of different compounds and ions in aqueous
solution is listed in a Standard Enthalpies of Formation at 25 0 C Table in
kJ/mole
example: ΔH0 f CO2 (g) = – 393.5 kJ/mole (from the table)

• Heat of formation, ΔH0 f value of the substances in their standard state is

equal to zero, 0 and can be omitted.
example: CH4(g) + 2 O2(g)  CO2(g) + 2 H2O (g)
ΔH0r =  ΔH0f (product/s) –  ΔH0f (reactant/s)
ΔH0r = ΔH0 f CO2(g) + ΔH0 f H2O (g) – ΔH0 f CH4(g) + ΔH0 f O2(g)
example : ΔH0 f O2(g) = 0
ΔH0r = ΔH0 f CO2(g) + ΔH0 f H2O (g) – ΔH0 f CH4(g) 81
 Heat of formation, ΔH0 f ….. General rule:
• Chemical equation must be balance. Coefficient of products and reactants in
the thermochemical equation must be taken into account.

example: CH4(g) + 2 O2(g)  CO2(g) + 2 H2O (g)

ΔH0r =  ΔH0f (product/s) –  ΔH0f (reactant/s)
ΔH0r = ΔH0 f CO2(g) + 2 ΔH0 f H2O (g) – ΔH0 f CH4(g) + ΔH0 f O2(g)
example : ΔH0f O2(g) = 0
ΔH0r = ΔH0 f CO2(g) + 2 ΔH0 f H2O (g) – ΔH0 fCH4(g)

82
 Heat of formation, ΔH0 f ….. General rule:
Ex.: Calculate the standard heat of reaction of the given chemical
equation: CH4(g) + 2 O2(g)  CO2(g) + 2 H2O (g)
Solution:
ΔH0r =  ΔH0f (product/s) –  ΔH0f (reactant/s)
ΔH0r = ΔH0 f CO2(g) + 2 ΔH0 f H2O (g) – ΔH0 fCH4(g) +2 ΔH0 f O2(g)
since: ΔH0 f O2(g) = 0
ΔH0r = ΔH0 f CO2(g) + ΔH0 f H2O (g) – ΔH0 fCH4(g)
substitute the value of ΔH0 f from the table:
ΔH0r = [1 mol(‐393.5 kJ/mole) + 2 mol(‐ 214.8kJ/mol)] – [1 mol(‐74.8 kJ/mol)]
ΔH0r = ‐ 748.3 kJ 83
Heat of formation, ΔH0 f
This principle can be used to determine :

• Heat of reaction, ΔH0r

• Heat of formation, ΔH0 f of one of the substances.

IN A GIVEN BALANCED CHEMICAL EQUATION.

Table 8.3
Table 8.3,
(Cont’d)
 Sample Problem:
1. Calculate the enthalpy of reaction for a given thermochemical equation:
2 CH3OH(l) + 3 O 2(g)  2 CO 2(g) + 4 H2O (l)
Solution:
ΔH0 =  ΔH0f (product/s) –  ΔH0f (reactant/s)

ΔH0 = 2 ΔH0f CO 2(g) + 4 ΔH0f H2O (l) – 2 ΔH0f CH3OH(l) + 3 ΔH0f O 2(g)
= 2 moles (– 393.5kJ/mol) + 4 mol (– 285.8 kJ/mol) – 2 mol (– 238.7 kJ/mol) + 0
= – 1,452.8 kJ

87
Sample problem:
2. The standard enthalpy change for the reaction: CaCO3(s)  CaO (s) + CO2 (g)
is 178.1 kJ/mol. Calculate the standard enthalpy of formation of CaCO3 (s)

• Given: ΔH0 = 178.1 kJ/mol

• Rqd.: ΔH0f CaCO3(s)
• Solution:
ΔH0 =  ΔH0f (product/s) –  ΔH0f (reactant/s)
ΔH0 = ΔH0f CO 2(g) + ΔH0f CaO (s) – ΔH0f CaCO3(s)
refer to the table for the values of ΔH0f CO 2(g) and ΔH0f CaO (s)
ΔH0f CO 2(g) = ‐393.5 kJ/mol ; ΔH0f CaO (s) = ‐635.1 kJ/mol
substitute the values:
178.1 kJ/mol = ‐393.5 kJ/mol + ‐635.1 kJ/mol ‐ ΔH0f CaCO3(s)
- ΔH0f CaCO3(s) = 178.1 kJ/mol + 1046.6 kJ/mol
- ΔH0f CaCO3(s) = 1,224.7 kJ/mol
ΔH0f CaCO3(s) = – 1,224.7 kJ/mol 88
 Sample Problem:
3. Benzene, C6H6 is used in a manufacture of plastics, is a carcinogen affecting
the bone marrow. Long term exposure has been shown to cause leukemia and
other blood disorders. The combustion of benzene is given by the following
equation:
C 6H 6 (l) + 7.5 O 2 (g)  6 CO 2(g) + 3 H2O (l) ΔH0 = – 3,267.4 kJ/mol
A) Calculate the heat of formation, ΔH0 f of benzene
B) Calculate the ΔH0 for the reaction:
12 CO 2(g) + 6 H2O (l)  2 C 6H 6 (l) + 15 O 2 (g)

89
Sample Problems:
4. Sodium carbonate is a white powder used in the manufacture of
glass. When hydrochloric is added to a solution of sodium carbonate,
carbon dioxide gas is formed. The equation for the reaction is:
2 H + (aq) + CO 3 2 – (aq)  CO 2(g) + H2O (l)
A) Calculate ΔH0 for the thermochemical reaction.
B) Calculate ΔH0 when 25.00 mL 0f 0.186 M HCl is added to sodium
carbonate.

90
Sample problem:
5. Calculate the standard enthalpy of formation of CuO (s) from the
given thermochemical equation:
CuO(s) + H2 (g)  Cu (s) + H2O (l) ΔH0 = – 129.7 kJ/ml

91
Sample problem:
6. Calculate for the enthalpy change, ΔH0 for the combustion of 1 mole
of ethanol:
C2H5OH(l) + 3 O 2(g)  2 CO 2(g) + 3 H2O (l)

92
Sample problem:
7. Calculate the standard enthalpy change for the combustion of 1 mol
of benzene, C 6H 6 from the given balanced chemical equation:
C 6H 6 (l) + 7.5 O 2 (g)  6 CO 2(g) + 3 H2O (l)

93
Sample Problem:
8. Calculate the standard enthalpy change for the combustion of 1 mol
of propane, C3H8 from the given balanced chemical equation:
C 3H 8 (g) + 5 O 2 (g)  3 CO 2(g) + 4 H2O (l)

94
 Sample Problem:
9. If not handled carefully, ammonium perchlorate can decompose violently
according to the thermochemical equation below.
2NH4ClO4(s)  N2(g) + Cl2(g) + 2O2(g) + 4H2O(g) ΔH0 = ‐ 375.6 kJ/mol
The enthalpy of formation of H2O(g) is ‐241.8 kJ/mol. Calculate the enthalpy
of formation of ammonium perchlorate.

95
Sample Problem:
10. Determine the heat of reaction for the combustion of ammonia,
4NH3(g) + 7O2(g)  4NO2(g) + 6H2O(l)
using molar enthalpies of formation.
molecule ΔHf (kJ/mol)
NH3(g) –45.9
NO2(g) +33.1
H2O(l) –285.8