Chapter 1:

THERMOCHEMISTRY

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 Contents:

 Exothermic and endothermic reactions.

 Energy profile.
 Enthalpy and enthalpy change.
 Calorimetry.
 Heat capacity and specific heat.
 Definition of heat of reaction and calculations.
 Hess”s law and calculation.

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 DEFINITION
 Thermochemistry is the study of
the energy changes taking place
during chemical reactions.

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 INTRODUCTION

 Every substance contains stored chemical energy,

called enthalpy, mainly by virtue of chemical bonds.

 Absolute enthalpy is hard to measure, but enthalpy

changes during reactions are easy to measure
because there will be an observable energy
exchange between the chemicals and the
surroundings.

 Energy cannot be created or destroyed, but can

change from one form to another.
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 Exothermic and Endothermic Reactions

 Every reaction can be considered as a series

of bond breaking steps followed by bond
forming steps.

 Bond breaking always requires energy.

 All bonds have different 'strengths' of

energies.
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 Exothermic and Endothermic Reaction (cont.)

 If bond forming releases more energy than was

required in the bond breaking, then overall energy is
released to the surroundings i.e. an exothermic
reaction ( H = negative)

 If bond forming releases less energy than was

required in the bond breaking, then overall energy
will have been absorbed from the surroundings
i.e. an endothermic reaction ( H = positive).

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 A chemical system and its surroundings.

the surroundings

the system

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 Exothermic and Endothermic Reactions
(cont.)
To measure energy changes of the reaction:
H = H products – H reactant = H final – H initial

 If H final < H initial : exothermic (has a negative H )

e.g. combustion, neutralisation, dissolving NaOH
pellets.

 If H final > H initial : endothermic (has a positive H )

e.g. mixing ammonium thiocyanate and barium
hydroxide crystals.
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 Energy Profile Diagrams
CH4 + 2O2 H2O(g)
Hinitial Hfinal
Enthalpy, H

Enthalpy, H
H < 0 heat out H > 0 heat in

CO2 + 2H2O H2O(l)

Hfinal Hinitial

A Exothermic process B Endothermic process

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

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 ENTRANCE SURVEY

All students must answer the entrance survey

questions for code CHM431 in i-learn portal

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 Sample Problem Drawing Enthalpy Diagrams and Determining
the Sign of H
PROBLEM: In each of the following cases, determine the sign of H, state
whether the reaction is exothermic or endothermic, and draw
and enthalpy diagram.
(a) H2(g) + 1/2O2(g) H2O(l) + 285.8kJ

(b) 40.7kJ + H2O(l) H2O(g)

PLAN: Determine whether heat is a reactant or a product. As a reactant,

the products are at a higher energy and the reaction is
endothermic. The opposite is true for an exothermic reaction
SOLUTION: (a) The reaction is exothermic. (b) The reaction is endothermic.
H2(g) + 1/2O2(g) (reactants) H2O(g) (products)

EXOTHERMIC H = -285.8kJ ENDOTHERMIC H = +40.7kJ

H2O(l) (products) H2O(l) (reactants)

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 Sample problem
(Drawing Enthalpy Diagrams and Determining
the sign of H)
When 1 mol of nitroglycerine decomposes, it
causes a violet explosion and releases 5.72 x
103 kJ of heat.
C3H5(NO3)3 (l) → 3CO2(g) + 5/2H2O(g) + 1/4O2(g) + 3/2N2(g)

Is the reaction exothermic or endothermic?

Draw an enthalpy diagram for it.

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 physical chemistry-CHM431- Dr noraini
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 Activation Energy

 Activation Energy of a
reaction, Ea, is the
minimum amount of
energy reactant
molecules must
possess in order to
form products.

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 Activation Energy
(Forward reaction)
On an Energy Profile, the activation
energy is measured from the energy of
the reactants to the peak of the energy
profile diagram.

The lower the activation energy, the

faster the reaction will proceed.

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 Activation Energy
(Reverse reaction)

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Measuring Enthalpy Changes, H
 Heats of Reaction, q can be measured in the laboratory
using a simple calorimeter made up of a polystyrene cup.
 Constant-Pressure Calorimeter
 H = E + PV , w = - PV
 E = q + w = q - PV
 At constant pressure, qp
 qp = E + PV = H (pg.232)
 So , H = qp

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 Coffee-cup calorimeter.

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 Sample Problem 6.4 Determining the Heat of a Reaction

PROBLEM: You place 50.0 mL of 0.500 M NaOH in a coffee-cup calorimeter at

25.000C and carefully add 25.0 mL of 0.500 M HCl, also at 25.000C.
After stirring, the final temperature is 27.210C. Calculate qsoln (in J) and
Hrxn (in kJ/mol). (Assume the total volume is the sum of the individual
volumes and that the final solution has the same density and specfic
heat capacity as water: d = 1.00 g/mL and c = 4.18 J/g*K)

PLAN: We need to determine the limiting reactant from the net ionic equation.
The moles of NaOH and HCl as well as the total volume can be
calculated. From the volume we use density to find the mass of the
water formed. At this point qsoln can be calculated using the mass, c, and
T. The heat divided by the M of water will give us the heat per mole of
water formed.

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 Measuring Energy Changes, E
 Using bomb calorimeter

 Constant-Volume Calorimeter

 At constant volume, qv

 W = PV = 0
 E = q + w = qv + 0 =qv
 So , E = qv

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 Figure 6.10

A bomb calorimeter

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 BOMB CALORIMETER

 For reactions involving gas

 Higher temperature
 -q reaction = +q calorimeter
 q reaction = Ccal x T (after bomb calorimeter
have been calibrated)

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 Sample Problem 6.5 Calculating the Heat of Combustion

PROBLEM: A manufacturer claims that its new dietetic dessert has “fewer
than 10 Calories per serving.” To test the claim, a chemist at the
Department of Consumer Affairs places one serving in a bomb
calorimeter and burns it in O2(the heat capacity of the
calorimeter = 8.15 kJ/K). The temperature increases 4.9370C.
Is the manufacturer’s claim correct?

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 Bomb Calorimeter
(Sample Problem)
A chemist burns 0.8650 g of graphite ( a form
of carbon) in a new bomb calorimeter, and
CO2 forms. If 393.5 kJ of heat is released per
mole of graphite and T increases 2.613 K,
what is the capacity of the bomb calorimeter?

(Answer:10.85 kJ/K)

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 Measuring heat Changes

heat changes (q)

= mass heated (g) x specific heat capacity (J g-1K-1) x
change in temperature (K)

or
q = m c T
Unit = kJmol-1
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 Heat Capacity

 When heat is supplied to a substance, the

temperature of the substance increase.

 The magnitude of the increase depends on

the heat capacity of the substance.

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 Heat Capacity (cont.)

heat capacity (unit: JK-1 or JC-1)

 is the amount of heat energy required to raise
the temperature of a substance by 1C or 1K
(Kelvin).

specific heat capacity (unit: Jg-1K-1)

 is the amount of heat required to raise the
temperature of 1g of the substance by 1C or
1K
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 Specific Heat Capacity (cont.)

For example:
The specific heat of water is 4.18 Jg-1K-1.

 This means that 4.18 J of heat is required to

raise the temperature of 1 g of water at 1K.

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 Table 6.2 Specific Heat Capacities of Some Elements, Compounds, and
Materials
Substance Specific Heat Substance Specific Heat
Capacity (J/g*K) Capacity (J/g*K)

Elements Materials
aluminum, Al 0.900 wood 1.76
graphite,C 0.711 cement 0.88
iron, Fe 0.450 glass 0.84
copper, Cu 0.387 granite 0.79
gold, Au 0.129 steel 0.45

Compounds
water, H2O(l) 4.184
ethyl alcohol, C2H5OH(l) 2.46
ethylene glycol, (CH2OH)2(l) 2.42
carbon tetrachloride, CCl4(l) 0.864
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 Sample Problem Finding the Quantity of Heat from Specific Heat
Capacity
PROBLEM: A layer of copper welded to the bottom of a skillet weighs 125 g.
How much heat is needed to raise the temperature of the
copper layer from 250C to 300.0C? The specific heat capacity
(c) of Cu is 0.387 J/g*K.

PLAN: Given the mass, specific heat capacity and change in temperature, we
can use q = c x mass x T to find the answer. T in 0C is the same as for
K.

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 Sample Problem

Exercise :
 Calculate the heat required to raise the
temperature of 250g of water from 28 C to 58  C

 Calculate the amount of heat needed to increase

the temperature of 250g of water from 20oC to
56oC.

 Calculate the specific heat capacity of copper given

that 204.75 J of energy raises the temperature of
15g of copper from 25oC to 60oC.
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 Sample Problem

 216 J of energy is required to raise the temperature

of aluminium from 15oC to 35oC. Calculate the mass
of aluminium.
(Specific heat capacity of aluminium is 0.90 JoC-1g-1).

 The initial temperature of 150g of ethanol was 22oC.

What will be the final temperature of the ethanol if
3240 J was needed to raise the temperature of the
ethanol?
(Specific heat capacity of ethanol is 2.44 JoC-1g-1).

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 Stoichiometry Of Thermochemical
Equations
 A thermochemical equation is a balanced
equation that includes the heat of reaction,
Hrxn.

 Hrxn value shown refers to the amounts

(moles) of substances and their states of
matter in that specific equations.

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 Stoichiometry Of Thermochemical
Equations
 Sign.
The sign of H depends on whether the
reaction is exothermic (-) or endothermic(+).
A forward reaction has the opposite sign of
the reverse reaction.

 Magnitude.
The magnitude of H is proportional to the
amount of substance reacting.

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 Sample Problem

Organic hydrogenation reactions, in which H2 and an

“unsaturated” organic compound, are used in the food,
fuel and polymer industries. In the simplest case,
ethene (C2H4) and H2 form ethane (C2H6).

If 137 kJ is given off per mole of C2H4 reacting, how

much heat is released when 15.0 kg of C2H6 forms?

( Answer:6.83 x 104 kJ)

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Types of Enthalpy Changes

Enthalpy of Combustion

is the heat released when 1 mole of a

substance is completely burnt in oxygen.

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 Enthalpy of Combustion
thermochemical equation.
CH4(g) + 2O2(g)  CO2(g) + 2H2O(l) H=-882kJ mol-1

CH3OH(l) + 1½O2(g)  CO2(g) + 2H2O(l) H=-715kJ mol-1

C2H5OH(l) + 3O2(g)  2CO2(g) + 3H2O(l) H=-1371kJ mol-1

C3H7OH(l) + 4½O2(g)  3CO2(g) + 4H2O(l) H=-2010kJ mol-1

C4H9OH(l) + 6O2(g)  4CO2(g) + 5H2O(l) H=-2670kJ mol-1

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 Enthalpy of Combustion
(Sample Problem)

The combustion of 1.8 g of ethanol, C2H5OH

increase 700 cm3 of water from25C to 38C.
Calculate the heat of combustion of ethanol.

(specific heat of water = 4.2 Jg-1K-1 and density of water = 1gcm-3)

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 Enthalpy of Solution

is the enthalpy change when 1 mole of

substance is completely dissolved in water

Na+OH-(s) + (aq)  Na+(aq) + OH-(aq) H=-40kJ mol-1

NH4+NO3-(s) + (aq)  NH4+(aq) + NO3-(aq) H=26kJ mol-1

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 Enthalpy of Neutralisation

is the heat released when 1 mole of water is formed during the

neutralisation of strong acid by an alkali

H+Cl-(aq) + Na+OH-(aq) Na+Cl-(aq) + H2O(l)

H+(aq) + Cl-(aq) + Na+(aq) + OH-(aq)  Na+(aq) + Cl-(aq) + H2O(l)

H+(aq) + OH-(aq)  H2O(l) H=-57kJ mol-1

The neutralisation of any strong acid by any alkali always produces

the same final equation and the same value for the change in
enthalpy.
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 Enthalpy of Neutralisation
(Sample Problem)
In a polystyrene cup, 100 cm3 1.0 M HCl and 100
cm3 of 1.0 M NaOH are mixed. Both solutions were
originally at 24.6C. After the reaction, the final
temperature is 31.3C. Calculate the enthalpy
change for the neutralization of HCl by NaOH.

( Assume that solution have a density of 1 gcm-3 and

specific heat capacity of 4.2 J g-1C-1).

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 The standard molar lattice enthalpy

is the heat energy released when one mole of

the ionic solid is formed from its gaseous ions
under standard conditions.

Na+ (g) + Cl- (g)  NaCl (s) H= negative

Hence, energy is required to separate the ions :
NaCl (s)  Na+ (g) + Cl- (g) H= positive

The greater the lattice energy the higher the melting

point of the compound.

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 Enthalpy of Formation

is the enthalpy change when 1 mole of a compound

is formed from its constituent elements in their
standard states (state at room temperature, 25°C and
at a pressure of 1 atmosphere) .

2C(s) + 3H2(g)  C2H6(g) Hf =-85kJ mol-1

2C(s) + H2(g)  C2H2(g) Hf =+237kJ mol-1

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Enthalpy of Formation(cont.)

 The standard enthalpy of formation of a

substance can be either positive or negative.

 The standard of formation of some substances

cannot be directly measured from experiment.

 So the enthalpy should be calculate by using

Hess’s law.

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 Writing Formation Equations

Write balances equations for the formation of 1

mol of each of the following compounds from
their elements in their standard states, and
include Hf (pg 242).

a) Silver chloride, AgCl a solid at standard

conditions.
b) CaO(s)
c) Hydrogen cyanide , HCN a gas at standard
states.
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 Enthalpy of Formation
(Sample Problem)
 Heat of combustion of benzene, C6H6 (l) is -3265 kJmol-1. The
heat of formation for H2O(l) and CO2(g) is -286 kJmol-1 and -
394 kJmol-1 respectively.

a) Write the thermochemical equation for the combustion of

benzene

b) Calculate the heat of formation of benzene, then write the

thermochemical equation for the formation of benzene.
( Ans : 43 kJmol-1)

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 Some Important Types of Enthalpy Change

heat of combustion (Hcomb)

C4H10(l) + 13/2O2(g) 4CO2(g) + 5H2O(g)

heat of formation (Hf)

K(s) + 1/2Br2(l) KBr(s)

heat of fusion (Hfus)

NaCl(s) NaCl(l)

heat of vaporization (Hvap)

C6H6(l) C6H6(g)

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 Hess's Law

 Definition
the enthalpy change of an overall process is the
sum of the enthalpy changes of its individual
steps.

 Application of Hess’s law

to calculate an unknown H which are impossible
to do in 1step, especially enthalpies of formation.

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 Sample Problem

Calculate the enthalpy of formation of

ethane given that the enthalpies of
combustion of carbon, hydrogen and
ethane are -394, -286 and -1542 kJ mol-1
respectively.

Target Equation:
2C(s) + 3H2(g)  C2H6(g)

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Standard Heats Of Reaction, Hrxn

 has been measured with all the reactants

and products in their standard states
( P= 1 atm ; solution = 1 M ; Temp = 298 K or
25C)

H = H products – H reactants

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 Sample Problem

Given the heat of formation , Hf of :

N2O4(g) = - 20 kJmol-1 ,
H2O(l) = - 286 kJmol-1 ,
N2H4(l) = + 50 kJmol-1.

Calculate the heat of reaction for :

N2O4(g) + 2N2H4(l)  3N2(g) + 4H2O(l)

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 Sample Problem

 Use the following information to find Hf of

methanol, CH3OH (l):
CH3OH (l) + 3/2O2(g) → CO2(g) + 2H2O(g)
Given Hcomb = -638.5 kJ

Hf of CO2(g) = - 393.5 kJmol-1

Hf of H2O(g) = - 241.8 kJmol-1
(answer: -238.6 kJ)
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 Figure 6.11

AMOUNT (mol) Summary of the relationship between

amount (mol) of substance and the heat
of compound A (kJ) transferred during a reaction.

AMOUNT (mol)
of compound B
molar ratio from
balanced equation

HEAT (kJ)

Hrxn (kJ/mol) gained or lost

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 Sample Problem 6.6 Using the Heat of Reaction (Hrxn) to Find
Amounts
PROBLEM: The major source of aluminum in the world is bauxite (mostly
aluminum oxide). Its thermal decomposition can be represented by
Al2O3(s) 2Al(s) + 3/2O2(g) Hrxn = 1676 kJ
If aluminum is produced this way, how many grams of aluminum can
form when 1.000x103 kJ of heat is transferred?

PLAN: SOLUTION:

heat(kJ) 1.000x103 kJ x 2 mol Al 26.98 g Al

1676 kJ 1 mol Al
1676kJ=2mol Al

mol of Al = 32.20 g Al
xM

g of Al

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 Sample Problem 6.7 Using Hess’s Law to Calculate an Unknown H

PROBLEM: Two gaseous pollutants that form in auto exhaust are CO and
NO. An environmental chemist is studying ways to convert them
to less harmful gases through the following equation:
CO(g) + NO(g) CO2(g) + 1/2N2(g) H = ?

Given the following information, calculate the unknown H:

Equation A: CO(g) + 1/2O2(g) CO2(g) HA = -283.0 kJ
Equation B: N2(g) + O2(g) 2NO(g) HB = 180.6 kJ

PLAN: Equations A and B have to be manipulated by reversal and/or

multiplication by factors in order to sum to the first, or target, equation.

SOLUTION: Multiply Equation B by 1/2 and reverse it.

CO(g) + 1/2O2(g) CO2(g) HA = -283.0 kJ
NO(g) 1/2N2(g) + 1/2O2(g) HB = -90.3 kJ
CO(g) + NO(g) CO2(g) + 1/2N2(g) Hrxn = -373.3 kJ
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 Table 6.5 Selected Standard Heats of Formation at 250C(298K)

Formula H0f(kJ/mol) Formula H0f(kJ/mol) Formula H0f(kJ/mol)

calcium silver
Cl2(g) 0
Ca(s) 0 Ag(s) 0
HCl(g) -92.3
CaO(s) -635.1 AgCl(s) -127.0
CaCO3(s) -1206.9 hydrogen
H(g) 218 sodium
carbon
H2(g) 0 Na(s) 0
C(graphite) 0
C(diamond) 1.9 nitrogen Na(g) 107.8
CO(g) -110.5 N2(g) 0 NaCl(s) -411.1
CO2(g) -393.5 NH3(g) -45.9 sulfur
CH4(g) -74.9 NO(g) 90.3 S8(rhombic) 0
CH3OH(l) -238.6 S8(monoclinic) 2
oxygen
HCN(g) 135 SO2(g) -296.8
O2(g) 0
CSs(l) 87.9
O3(g) 143 SO3(g) -396.0
chlorine H2O(g) -241.8
Cl(g) 121.0 H2O(l) -285.8
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 Sample Problem 6.8 Writing Formation Equations

PROBLEM: Write balanced equations for the formation of 1 mol of the following
compounds from their elements in their standard states and include
H0f.
(a) Silver chloride, AgCl, a solid at standard conditions.
(b) Calcium carbonate, CaCO3, a solid at standard conditions.

(c) Hydrogen cyanide, HCN, a gas at standard conditions.

PLAN: Use the table of heats of formation for values.

SOLUTION:

(a) Ag(s) + 1/2Cl2(g) AgCl(s) H0f = -127.0 kJ

(b) Ca(s) + C(graphite) + 3/2O2(g) CaCO3(s) H0f = -1206.9 kJ

(c) 1/2H2(g) + C(graphite) + 1/2N2(g) HCN(g) H0f = 135 kJ

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 Figure 6.13

The general process for determining H0rxn from H0f values.

Elements

decomposition
Enthalpy, H

-H0f H0f

formation
Reactants
Hinitial

H0rxn

Products
Hfinal

H0rxn = S mH0f(products) - S nH0f(reactants)

physical chemistry-CHM431- Dr noraini

9/12/2017 10:06 AM hamzah 58
 Sample Problem 6.9 Calculating the Heat of Reaction from Heats of
Formation
PROBLEM: Nitric acid, whose worldwide annual production is about 8 billion
kilograms, is used to make many products, including fertilizer, dyes,
and explosives. The first step in the industrial production process is
the oxidation of ammonia:
4NH3(g) + 5O2(g) 4NO(g) + 6H2O(g)

Calculate H0rxn from H0f values.

PLAN: Look up the H0f values and use Hess’s Law to find Hrxn.

SOLUTION: Hrxn = S mH0f (products) - S nH0f (reactants)

Hrxn = [4(H0f NO(g) + 6(H0f H2O(g)] - [4(H0f NH3(g) + 5(H0f O2(g)]

= (4 mol)(90.3 kJ/mol) + (6 mol)(-241.8 kJ/mol) -

[(4 mol)(-45.9 kJ/mol) + (5 mol)(0 kJ/mol)]

Hrxn = -906 kJ
physical chemistry-CHM431- Dr noraini
9/12/2017 10:06 AM hamzah 59