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ThermoChemistry

Thermochemistry involves the relationship between chemical reactions and energy changes. There are different types of energy including kinetic, potential, chemical, and nuclear. The first law of thermodynamics states that energy cannot be created or destroyed, only changed from one form to another. Enthalpy is a measurement of the total energy of a system and can be used to determine if a reaction is endothermic or exothermic. Calorimetry is used to directly measure the heat change of a reaction. Standard enthalpy values allow for calculation of enthalpy change based on reaction stoichiometry.

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15 views28 pages

ThermoChemistry

Thermochemistry involves the relationship between chemical reactions and energy changes. There are different types of energy including kinetic, potential, chemical, and nuclear. The first law of thermodynamics states that energy cannot be created or destroyed, only changed from one form to another. Enthalpy is a measurement of the total energy of a system and can be used to determine if a reaction is endothermic or exothermic. Calorimetry is used to directly measure the heat change of a reaction. Standard enthalpy values allow for calculation of enthalpy change based on reaction stoichiometry.

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JOSHUA NYANGENA
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Thermochemistry

1
Thermochemistry
• Thermochemistry – the part of thermodynamics that
involves the relationship between chemical reactions
and energy changes
I. Energy
Energy: the ability (or capacity) of a system to do work or supply
(or produce) heat.
(1) Kinetic energy is the energy associated with motion; the
faster an object moves, the more kinetic energy it has. There is
an equation which governs this:
K.E. = (1/2) mv2 m means mass and v is velocity.

Since any mass, time or distance unit could be used, it has been
agreed to standardize on specific units for these three
quantities and they are the kilogram, second and meter.
Inserting them in the above equation gives:
(kg) (m)2/ (s)2
This unit has been given a name: Joule.
The Joule is the standard metric (or SI) unit for all energy.
Energy Units
– Joule (J) – SI unit of energy (1J = 1 kg·m2/s2)
– calorie (cal) – the amount of energy required to raise 1 g of water by 1oC.
• 1 cal = 4.184 J
I. Energy
(2) Potential energy is energy that is stored by virtue of position.
There are several different types of storage, of which these four
are examples.

(a) Gravitational - this is the most familiar. A rock poised to


roll down a hill has potential energy. A ball thrown into the air
gains more and more potential energy as it rises. The higher in
the gravity field you go, the more potential energy you gain.

(b) Electrical - in certain materials, you can remove electrons


from one area and send them to another. The area losing the
electrons becomes more and more positive and the area gaining
them becomes negative. The greater and greater the charge
difference, the more energy is stored within the system.
I. Energy

(c) Chemical - this is slightly more complex. Certain chemicals have bonds
which require little energy to break. This energy must be put into the bond to break
it. However, during the course of the chemical reaction, new bonds form which give
off MORE energy than that which was put in.

- The positional aspect comes from first breaking bonds between atoms
(which takes energy) and then rearranging the atoms in new positions to form new
bonds (which gives off energy).

- If you get back more than you put it, this is called exothermic.

- If you get back less than you put in, this is called endothermic.

(d) Nuclear - the famous equation E = mc2 governs this source of potential
energy. We can consider the mass itself to be potential energy, since it can be
converted from a form not being used (while it is the mass), to kinetic energy. This
type of potential energy is released (in measurable amounts) during radioactive
decay, fission and fusion.
II. Work (w)
• The usual definition of work is: a force acting
over a distance
• A more technical definition is: the transfer of
energy from one mechanical system to
another.
III. Heat (q)
There is a lot of misunderstanding about what heat is: heat is not a thing,
heat is a process.

The definition: heat is the transfer of energy between two objects due to
temperature differences.

Notice that the name of the transfer process is heat. What gets transfered
is energy. Heat is NOT a substance although it is very convenient to think
of it that way. In fact, it used to be thought that heat was a substance.

There is a circular nature to the definitions used:


(a) energy does work or produces heat, but
(b) heat is a transfer of energy.
IV. Temperature
• The temperature is absolute temperature, measured
in Kelvins.
• The definition: temperature is a property which is
directly proportional to the kinetic energy of the
substance under examination.
• Another useful definition: temperature is the
property which determines the direction heat will
flow when two objects are brought into contact.
First Law of Thermodynamics
• Energy can be converted from one form to
another, but it is neither created nor destroyed.
• To heat your home, chemical energy needs to be
converted to heat.
• Sunlight is converted to chemical energy in green
plants.
• There are MANY more examples of conversion of
energy.
Definitions: System and
Surroundings
• The portion of the universe
that we single out to study is
called the system (here, the
hydrogen and oxygen
molecules).
• The surroundings are
everything else (here, the
cylinder, piston and
everything beyond).
Internal Energy
• The internal energy of a system is the sum of all
kinetic and potential energies of all components of
the system; we use E to represent it.
• We generally don’t know E, only how it CHANGES
(ΔE).
Internal Energy
By definition, the change in internal energy, ΔE, is the
final energy of the system minus the initial energy of
the system:
ΔE = Efinal − Einitial
Changes in Internal Energy
• When energy is
exchanged between
the system and the
surroundings, it is
exchanged as either
heat (q) or work (w).
• That is, ΔE = q + w.
ΔE, q, w, and Their Signs
Work
• We can measure the work done by the gas if the
reaction is done in a vessel that has been fitted with a
piston: w = −PΔV
• The work is NEGATIVE because it is work done BY the
system.
Enthalpy
• If a process takes place at constant pressure
(and we usually work at atmospheric pressure)
and the only work done is this pressure–volume
work, we can account for heat flow during the
process by measuring the enthalpy (H) of the
system.
• Enthalpy is the internal energy plus the product
of pressure and volume:
H = E + PV
Enthalpy
• When the system changes at constant
pressure, the change in enthalpy, ΔH, is
ΔH = Δ (E + PV)
• This can be written
ΔH = ΔE + PΔV
Enthalpy
• Since ΔE = q + w and w = −PΔV, we can
substitute these into the enthalpy
expression:
ΔH = ΔE + PΔV
ΔH = (q + w) − w
ΔH = q
• So, at constant pressure, the change in
enthalpy is the heat gained or lost.
Endothermic and Exothermic

• A process is
endothermic when
ΔH is positive.
• A process is
exothermic when
ΔH is negative.
Enthalpy of Reaction

The change in enthalpy,


ΔH, is the enthalpy of the
products minus the
enthalpy of the reactants:

ΔHrxn = Hproducts − Hreactants


Enthalpy of Reaction
This quantity, ΔHrxn, is called the enthalpy of
reaction, or the heat of reaction.

Note that the enthalpy change for a reaction is equal in magnitude, but
opposite in sign, to ΔH for the reverse reaction.
Calorimetry
• Since we cannot know the
exact enthalpy of the
reactants and products, we
measure ΔH through
calorimetry, the
measurement of heat flow.
• The instrument used to
measure heat flow is called a
calorimeter.
Heat Capacity and Specific Heat
The amount of energy required to raise the temperature of a
substance by 1 K (1 °C) is its heat capacity. If the amount of the
substance heated is one gram, it is the specific heat. If the amount
is one mole, it is the molar heat capacity.
Constant Pressure Calorimetry
• By carrying out a reaction in aqueous
solution in a simple calorimeter, the
heat change for the system can be found
by measuring the heat change for the
water in the calorimeter.
• The specific heat for water is
4.184 J/g∙K. We use this value for dilute
solutions.
• We can calculate ΔH for the reaction
with this equation:
qsoln = Cs × msoln × ΔT = –qrxn
Enthalpies of Formation
An enthalpy of formation, ΔHf, is defined as
the enthalpy change for the reaction in
which a compound is made from its
constituent elements in their elemental
forms.
Standard Enthalpies of Formation
Standard enthalpies of formation, ΔHf°, are
measured under standard conditions (25 °C and
1.00 atm pressure).
Calculation of ΔH
We can use Hess’s law in this way:

ΔH = ΣnΔHf,products – ΣmΔHf°,reactants

where n and m are the stoichiometric


coefficients.
Calculation of ΔH using Values from
the Standard Enthalpy Table
C3H8(g) + 5 O2(g) 3 CO2(g) + 4 H2O(l)

ΔH = [3(−393.5 kJ) + 4(−285.8 kJ)] – [1(−103.85 kJ) + 5(0 kJ)]


= [(−1180.5 kJ) + (−1143.2 kJ)] – [(−103.85 kJ) + (0 kJ)]
= (−2323.7 kJ) – (−103.85 kJ) = −2219.9 kJ

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