THERMOCHEMISTRY

CHAPTER 1
MDM. HAIRUL AMANI
BINTI
ABDUL HAMID

CHM471 Physical Chemistry 1

LEARNING OUTCOMES
At the end of this topic, you should be able to:
1. Explain the concept of chemical energy,
potential energy, work, heat, heat capacity,
specific heat capacity and Hesss Law
2. Draw energy profiles diagram of
exothermic and endothermic reactions.
3. Distinguish the differences between the
reaction in a simple and bomb calorimeter
4. Calculate the heat of reaction, enthalpy of
combustion and enthalpy of formation.
2
 Thermochemistry

The study of the

Is a branch of
energy transferred
thermodynamics
as heat during the
course of chemical
reactions
A reaction vessel and its
contents form a system, and
chemical reactions result in the
exchange of energy between
the system and the
surroundings
3
WORK
is done to achieve motion against an
opposing force;
Is the transfer of energy resulting from a process
that causes or utilize motion of atoms in the
surroundings
Work = force x distance

4
WORK
Example:

1.The process of raising a weight against

the pull of gravity

- work is done on a system, when molecules

in the surroundings are used to transfer
energy to it in an organized way as the atoms
in a weight are lowered.

5
WORK
Example:
.
2. A chemical reaction that drives an
electric current through a resistance

- work is done on a system, when molecules

in the surroundings are used to transfer
energy to it in an organized way as a current
of electrons is passed.

6
ENERGY
Is the capacity of a system to do work

When work is done on an isolated system

(for example by compressing a gas),
- the capacity of the system to do work is
increased; the energy of the system is increased.

When the system does work

(i.e. when the piston moves out)
- the energy of the system is reduced and it can do
less work than before.
7
 ENERGY

KINETIC CHEMICAL
ENERGY ENERGY
POTENTIAL
ENERGY

8
 KINETIC ENERGY ENERGY OF MOTION

POTENTIAL ENERGY ENERGY DUE

CONDITION/POSITION/COMPOSITION

CHEMICAL ENERGY ENERGY STORED WITHIN

THE STRUCTURAL UNITS OF CHEMICAL
SUBSTANCES.

9
HEAT
When the energy of a system changes as a result
of a temperature difference between the system
and its surroundings we say that energy has been
transferred as heat.

Boundaries that do permit the transfer of energy

as heat are called diathermic;
those that do not are called adiabatic.

10
 SYSTEM

SYSTEM refer to the substances involved in a

reaction.

SURROUNDINGS - - Those parts around the system

that interact with the system.

11
TYPES OF SYSTEM

SYSTEM

OPEN
CLOSED ISOLATED
SYSTEM
SYSTEM SYSTEM

12
 OPEN SYSTEM

EXCHANGING MATTER AND ENERGY WITH ITS

SURROUNDINGS

13
 CLOSED SYSTEM

- EXCHANGE ENERGY BUT NOT MATTER

14
 ISOLATED SYSTEM

EXCHANGE NEITHER ENERGY NOR MATTER

INSULATOR

15
STATE OF A SYSTEM

DESCRIBING THE CONDITION OF THE

SYSTEM BY GIVING THE VALUES OF A
SUFFICIENT SET OF NUMERICAL
VARIABLES.

16
STATE FUNCTION
A state function (state variable) is a property
of a system that depends only on the current state
(condition) of the system, not on the way in which
the system acquired that state (independent of
path).

A state function describes the equilibrium state of

a system.

Example: internal energy (U), enthalpy (H) and

entropy (S) are state quantities because they
describe quantitatively an equilibrium state of a
thermodynamic system, irrespective of how the
system arrived in that state.
17
 EXOTHERMIC REACTIONS

Any reaction that releases energy as heat into its

surroundings.
Combustion reactions.

Heat flow : System Surroundings

- due to lowering of potential energy of reaction system

PE PDTS < PE RXTS q<0

18
ENERGY LEVEL DIAGRAM FOR
EXOTHERMIC REACTION
H

REACTANTS

H = - x kJ

PRODUCTS

REACTION PATHWAY
19
ENERGY PROFILE DIAGRAM

20
ENDOTHERMIC REACTION
Any reaction that absorbs energy from its
surroundings as heat.
Example - the vaporization of water.

Heat is supplied to the system by the

surrounding
Energy flow into the system as heat is used to
increase potential energy of system
PE PDTS > PE RXTS q>0

21
ENERGY LEVEL DIAGRAM FOR
ENDOTHERMIC REACTION
H
PRODUCTS

H = +x KJ

REACTANTS

REACTION PATHWAY

22
ENERGY PROFILE DIAGRAM

23
 QUESTION
1) Sketch a potential-energy diagram to show the reaction
profile of the chemical reaction. The activation energry =
100 kJ/mole.

CO(g) + NO2(g) CO2(g) + NO(g) H = -226 kJ mol-1

a) Indicate the activation energy as well as the enthalpy

change of the reaction
b) What is the activation energy for the reverse
reaction?

24
INTERNAL ENERGY - U
is the total energy of a system.
Is a state function - its value depends only on the
current state of the system and is independent of how
that state has been prepared.
U is the change in internal energy when a system
changes from an initial state i with internal
energy Ui to a final state f of internal energy Uf

U = Uf Ui
25
UNIT OF INTERNAL ENERGY
U is an extensive property of a system and is
measured in joules (1 J = 1 kg m2 s2).
Um,(molar internal energy) is the internal energy
divided by the amount of substance in a
system, Um = U/n; it is an intensive property and
commonly reported in kilojoules per mole (kJ mol1).
(extensive: it is directly proportional to the amount of
material in the system, eg: Mass and volume
Intensive: it does not depend on the system size or the
amount of material in the system, eg:
temperature,refractive index,density )
26
FIRST LAW OF THERMODYNAMICS
The internal energy of a system may be changed
by doing work on the system or by heating (i.e
transfer of energy by doing work or transfer of
energy by heating)

ifa system is isolated from its surroundings, then

no change in internal energy takes place.

Given by the mathematical statement of the First

Law:

U = q + w
27
 FIRST LAW OF THERMODYNAMICS
U = Q + W

(w= work done, q= heat transferred)

q = + (heat flows into the system from the surrounding)
q = - (heat flows from the system to the surroundings)
w = + (work is done on the system by the surrounding)
w = - ( system does work on the surroundings)

The internal energy is constant in an isolated system (for

which q = 0 and w = 0)

28
EXAMPLE
1. If an electric motor produced 15 kJ of energy
each second as mechanical work and lost 2 kJ
as heat to the surroundings, what is the
change in the internal energy of the motor each
second?
U = q + w
U = 2 kJ 15 kJ = 17 kJ

29
EXAMPLE
2.Suppose that, when a spring was wound, 100 J of
work was done on it but 15 J escaped to the
surroundings as heat. What is the change in
internal energy of the spring ?

U = q + w
U = 15 J + 100 J = +85 J

30
 Example:
Calculate U for a system undergoing an
endothermic process in which 15.6 kJ of heat flows
and where 1.4 kJ of work is done on the system.

Using, U = q + w
given q = +15.6 w = + 1.4 kJ
U = 15.6 + 1.4 = 17.0 kJ

The system has gained 17.0 kJ of energy.

31
EXPANSION WORK
Expansion work is proportional to the
external pressure.
Free expansion (against zero pressure) does
no work.
The work of expansion against constant
pressure is proportional to that pressure and
to the change in volume.
To achieve reversible expansion, the
external pressure is matched at every stage
to the pressure of the system.
The work of reversible, isothermal
expansion of a perfect gas is a logarithmic
function of the volume.
32
EXPANSION WORK
Expansion work is
proportional to the
external pressure.
Figure 2.6 When a
piston of area A moves
out through a distance
dz, it sweeps out a
volume dV =Adz. The
external pressure pex is
equivalent to a weight
pressing on the piston,
and the force opposing
expansion is F = pexA. 33
dw = -Fdz (note: W = F x d , F = P x A,
Since F = pextA V = A x h)
dw = pexAdz dV = Adz
= pex dV
To obtain the total work done when the volume changes
from an initial value Vi to a final value Vf we integrate
this expression between the initial and final volumes:

V = Vf Vi, w = - pexV
(If the system is compressed Vf < Vi)
34
w = - pexV
(If the system is compressed Vf < Vi)
Expansion work is done by the system
to the surroundings, w = -
Compression work is done to the system by the
surroundings, w = +

For expansion of a gas,

w = - PV
Since U = q + w
= q + (-pexV) If V = 0 (adiabatic
U = qv bomb calorimeter)
(The heat change of a reaction at constant volume)
35
SPECIFIC HEAT CAPACITY (C)

Is the amount of heat required to

raise temperature of a 1g of
substance by 1oC or K. Unit JoC-
1g-1 or JK-1g-1

36
HEAT CAPACITY (C)

An extensive property.
Is the amount of heat needed to raise
temperature of a given quantity of
substance by 1oC or K. Unit JoC-1 or
JK-1

37
 The heat capacity (C) is used to relate a change in internal
energy to a change in temperature of a
constant-volume system

For infinitesimal change of U and T:

dU = CvdT (at constant volume)
For a measurable change of U and T:
U = CvT

A change in internal energy can be identified with the heat

supplied at constant volume: (U = qv )
q = CvT

A large heat capacity implies that, for a given quantity of

energy transferred as heat, there will be only a small
increase in temperature (the sample has a large capacity for
heat).

38
ENTHALPY (H)
- IS THE INTERNAL ENERGY PLUS THE
PRODUCT OF PRESSURE AND VOLUME.

H = U + PV

U = INTERNAL ENERGY
P = PRESSURE
V = VOLUME

H, U, P AND V ARE STATE PROPERTIES

39
SINCE U = q + w
IF PROCESS CARRIED UNDER CONSTANT
PRESSURE AND ONLY EXPANSION OF VOLUME
ALLOWED
w = - PV
U = - PV + q .. (1)

q = U + PV

q IS HEAT RELEASED AT CONSTANT PRESSURE

40
SINCE H = U+ PV
H = U + PV AT CONSTANT PRESSURE
SINCE U = - PV + q (1)
H = U + PV

= - PV + q + PV
=q
H = qp

41
ENTHALPY (H)
Energy transferred as heat at constant
pressure is equal to the change in enthalpy
of a system. (qp = H)
Enthalpy changes are measured in a
constant-pressure calorimeter.

42
CALORIMETRY
DEVICE USED CALORIMETER

1. CONSTANT PRESSURE CALORIMETERY

- USE COFFEE CUP CALORIMETER

HEAT CHANGE = ENTHALPY

IN SYSTEM CHANGE
qp = H

43
SIMPLE CALORIMETER

44
SIMPLE CALORIMETER
ANOTHER SIMPLE CALORIMETER (NOT FOR
COMBUSTION) COFFEE CUP CALORIMETER

45
2. Constant Volume Calorimetery.
- Adiabatic Bomb Calorimter.

HEAT CHANGE = INTERNAL ENERGY

IN SYSTEM CHANGE
qV = U

46
ADIABATIC BOMB CALORIMETER

47
AMOUNT OF HEAT RELEASED =
q = mcT
OR
q = CT

q REACTION = (qCALORIMETER + qsolution )

= ( CT + mcT)

48
DETERMINING HEAT OF REACTION
50 mL of 0.5M NaOH in a coffee-cup calorimeter
at 25oC is added to 25mL of 0.5M HCl at 25oC.
After stirring, the final temperature is 27.21oC.
Calculate qsolution (in J) and Hrxn (in kJ/mol)

(Density of solution: 1 g/mL and specific heat

capacity of water = 4.184 J/g.K)

49
Answer:
Heat of reaction = heat gained by mixture + heat gained
by calorimeter.
q = (25 + 50) X 4.18 X (27.21 25)
= 692.84 J
= 0.69 kJ
nH+ = 0.5 M x 0.250 L = 0.0125 mol
nOH- = 0.5 x 0.050 L = 0.025 mol
H+ is limiting reactant.
H = q/n =- 0.69/0.0125 =- 55.4 kJ mol-1

50
ENTHALPIES OF CHEMICAL CHANGE

enthalpy changes that accompany chemical

reactions

51
STANDARD ENTHALPY CHANGE OF
REACTION

A FEW TYPES TO OBSERVE:

1. STANDARD ENTHALPY OF FORMATION

2. STANDARD ENTHALPY OF COMBUSTION

3. STANDARD ENTHALPY OF
NEUTRALISATION

52
STANDARD ENTHALPY OF
FORMATION HF

ENTHALPY CHANGE WHEN 1 MOLE OF PURE

COMPOUND IS FORMED FROM ITS
ELEMENTS UNDER STANDARD
CONDITIONS.

H2(g) + O2(g) H2O(l) Hf=-285.5kJmol-1

1mol

53
STANDARD ENTHALPY OF
FORMATION HF

H2(g) + O2(g) H2O(g) H=-241.8kJmol-1

H Hf

H2O(g) IS NOT IN ITS NORMAL PHYSICAL STATE

AT STANDARD CONDITIONS.

54
STANDARD ENTHALPY OF
FORMATION HF
2H2(g) + O2(g) 2H2O(l) H=-571kJmol-1
2 mol
H Hf

ONLY ONE MOLE OF COMPOUND SHOULD BE

FORMED IN THE REACTION.

FOR ALL ELEMENTS Hf = 0

NO HEAT CHANGE INVOLVED WHEN ELEMENT
IS FORMED.
55
TABLE 2.8 STANDARD ENTHALPIES OF FORMATION
OF INORGANIC COMPOUNDS AT 298 K

56
USING HF DATA TO CALCULATE H

Hr = nPHf(PRODUCT) - nRHf(REACTANT)

EXAMPLE:
THE Hf FOR CO2, C2H6 AND H2O ARE -393, -85 AND
-286 kJmol-1. Calculate H for the following
reaction:
C2H6(g) + 7/202(g) 2CO2(g) + 3H2O(l)

57
ANSWER TO THE QUESTION

C2H6(g) + 7/202(g) 2CO2(g) + 3H2O(l)

Hr = nPHf(PRODUCT) - nRHf(REACTANT)
= [2HfCO2+ 3HfH2O] [HfC2H6 +
7/ H O ]
2 f 2
= [(2 X -393) + (3 X -286)] [-85 + 0]
= [-786 + -858] + 85
= -1559 kJmol-1

58
STANDARD ENTHALPY OF
COMBUSTION HC

ENTHALPY CHANGE WHEN ONE MOLE OF

PURE SUBSTANCE IS COMPLETELY
BURNED IN EXCESS OXYGEN UNDER
STANDARD CONDITIONS.

C2H6(g) + 7/202(g) 2CO2(g) + 3H2O(l)

HC= -1559 kJmol-1

59
EQUATION FOR HC
C = mc

WHERE m = MASS OF SUBSTANCE

AMOUNT OF HEAT RELEASED OR

ABSORBED:
q = mct OR q = Ct

HC= q/n WHERE n = NO OF MOLES OF

SUBTANCE BURNT 60
TO DETERMINE HC
When C2H5OH is burnt using the simple
calorimeter, the following results are obtained:
Mass of C2H5OH before combustion: 400.0g
Mass of C2H5OH after combustion: 398.5g
Mass of water in the metal calorimeter:
500g
Increase in temperature : 12.95 OC
Specific heat capacity of water: 4.18 J g-1K-1
Calculate Hc of C2H5OH
61
ANSWER TO THE QUESTION
q = mct
= 500 X 4.18 X 12.95
= 27,066 J = 27.07 kJ

Mass of ethanol = 400-398.5 = 1.5g

n of C2H5OH burnt = mass/molar mass
= 1.5g/46 gmol-1
= 0.0325 mol
Hc =q/n=27.07 kJ/ 0.0325 mol = -830
kJmol-1 62
TO DETERMINE HC
1.435g of napthalene, C10H8, was burned in a bomb
calorimeter. The temperature of water rose from
20.28 oC to 25.95 oC. If heat capacity of the bomb
plus water was 10.17 kJoC-1, calculate Hc of
naphthalene.

m=1.435g Mr = 128
C = 10.17 kJoC-1
t = 25.95-20.28 = 5.67 oC

63
ANSWER TO THE QUESTION
q = Ct
= 10.17 kJoC-1 x 5.67 oC
= 57.66 kJ
n of C10H8 = m/Mr = 1.435g/ 128gmol-1
= 0.011 mol
Hc = q/n
= 57.66kJ/0.011mol
= - 5241.8 kJmol-1

64
STANDARD ENTHALPY OF
NEUTRALISATION HNEUT
IS THE ENTHALPY CHANGE WHEN 1 MOLE
OF H+ FROM ACIDS REACT WITH 1 MOLE OF
OH- FROM AN ALKALI TO FORM 1 MOLE OF
WATER MOLECULES UNDER STANDARD
CONDITIONS.

NaOH(aq) + HCl(aq) NaCl(aq) + H2O(l)

OH- + H+ H2O Hneut = -56.2 kJmol-1

65
TO DETERMINE HNEUT
100 ml of 0.5M HCl was mixed with 100 ml of 0.5M
NaOH in a coffee cup calorimeter. The initial
temperature of both solutions was 22.5 oC and
the final temperature of the mixed solution was
25.9 oC. Calculate the Hneut of the reaction.

66
ANSWER TO THE QUESTION
qrxn = qsoln
qsoln = mct
= (100g + 100g) x 4.18 x (25.9-22.5)
= 2842.4J
= - 2.84 kJ (qrxn)
n of solution =Mv/1000 = 0.5 x 100/1000
= 0.05 mol
Hneut = - 2.84kJ/0.05mol = -56.8 kJmol-1

67
HESSS LAW

STATES THAT WHEN REACTANTS ARE

CONVERTED TO PRODUCTS, THE CHANGE
IN ENTHALPY IS THE SAME WHETHER THE
REACTION TAKES PLACE IN ONE STEP OR
IN A SERIES OF STEPS.

IMPORTANT WHEN H DIFFICULT TO CARRY

OUT DIRECTLY IN A CALORIMETER

68
HESS LAW
Route 1
A+B H1
C+D

H3
H2
E H1= H2+ H3

Route 2

Hess law states that the total enthalpy change accompanying

a chemical reaction is independent of the route by which the
chemical reaction takes place.
THERMOCHEMICAL EQUATIONS

1. SPECIFY PHYSICAL STATES

CH4(g) + 2O2(g) CO2(g) + 2H2O(g)
H=-802.4 kJ mol-1

CH4(g) + 2O2(g) CO2(g) + 2H2O(l)

H=-890.4 kJ mol-1
2H2O(l) 2H2O(g) H=88.0 kJ mol-1

70
THERMOCHEMICAL EQUATIONS

2.IF MULTIPLY OR DIVIDE BOTH SIDES BY

FACTOR N, H MUST ALSO CHANGE BY SAME
FACTOR.

H2O(s) H2O(l) H=6.01 kJ mol-1

2H2O(s) 2H2O(l) H=2 X 6.01 kJ mol-1

71
THERMOCHEMICAL EQUATIONS

3.WHEN REVERSE A CHEMICAL EQUATION,

CHANGE REACTANT PRODUCTS,
PRODUCTS REACTANTS.
VALUE OF H REMAINS THE SAME BUT THE
SIGN CHANGES.

2H2O(l) 2H2O(g) H=88.0 kJ mol-1

2H2O(g) 2H2O(l) H= - 88.0 kJ mol-1

72
APPLICATION OF HESSS LAW

DETERMINE THE Hf OF CO IN THE

FOLLOWING EQUATION:
C(graphite) + O2(g) CO(g) Hf=?

Given the following reactions:

1) C(graphite) + O2(g) CO2(g) H1=-393.5 kJ
mol-1
2) CO(g) + O2(g) CO2(g) H2=-283.0 kJ
mol-1

73
ANSWER TO THE QUESTION
C(graphite) + O2(g) CO(g) Hf=?

1) C(graphite) + O2(g) CO2(g) (maintain)

2) CO(g) + O2(g) CO2(g) (reverse)

1) C(graphite) + O2(g) CO2(g) H1=-393.5 kJ mol-1

2) CO2(g) CO(g) + O2(g) H2=+283.0 kJ mol-1

C(graphite) + O2(g) CO(g)
Hf= H1 +H2
= -110 kJ mol-1

74
EXAMPLE
The standard reaction enthalpy for the hydrogenation
of propene

CH2= CHCH3(g) + H2(g) CH3CH2CH3(g)

is 124 kJ mol1. The standard reaction enthalpy for

the combustion of propane

CH3CH2CH3(g) + 5O2(g) 3 CO2(g) + 4 H2O(l)

is 2220 kJ mol1. Calculate the standard enthalpy

of combustion of propene.

75
TABLE 2.6 STANDARD ENTHALPIES OF FORMATION
AND COMBUSTION OF ORGANIC COMPOUNDS AT 298
K

76
ANSWER TO QUESTION
The combustion reaction we require is

This reaction can be recreated from the

following sum:

77
ADDITIONAL QUESTION
Calculate the enthalpy of hydrogenation of
benzene from its enthalpy of combustion and the
enthalpy of combustion of cyclohexane.
Hc (cyclohexane) C6H12= 3930 kJ/mol
Hc (benzene) C6H6 = 3273 kJ/mol

[205 kJ mol1]

78