Chapter 1:

THERMOCHEMISTRY

* 1
 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.

* 2
 DEFINITION
■ Thermochemistry is the study of
the energy changes taking place
during chemical reactions.

* 3
■ The relationship between chemical reactions and
energy changes is known as thermochemistry

■ The SI unit for energy is the Joule (J). Traditionally

energy changes accompanying chemical reactions have
been expressed in calorie

1 calorie = 4.184 J, kcal=1000 cal

 INTRODUCTION

■ Every substance contains stored chemical energy,

called enthalpy, mainly by 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.

* 5
 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.
* 6
 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 ( ΔH = 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 ( ΔH = positive).

* 7
 A chemical system and its surroundings.

the surroundings

the system

* 8
 Exothermic and Endothermic Reactions
(cont.)
To measure energy changes of the reaction:
ΔH = H products – H reactant = H final – H initial

■ If H final < H initial : exothermic (has a negative ΔH )

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

■ If H final > H initial : endothermic (has a positive ΔH )

e.g. mixing ammonium thiocyanate and barium
hydroxide crystals.

* 9
 Energy Profile Diagrams
CH4 + 2O2 H2O(g)
Hinitial Hfinal
Enthalpy, H

Enthalpy, H
ΔH < 0 heat out ΔH > 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)

* 10
Exothermic Reaction ( H products < H reactants)

2SO2(g) + O2(g)  2SO3(g) , H = - 197kJ

2SO2(g) + O2(g)
H = H products – H reactants

energy reactants
H = - 197 kJ (heat released)

H = - 197 kJ
(heat released)
2SO3(g)

products

Exothermic Reaction
Endothermic Reaction ( H products > H reactants)

2SO3(g)  2SO2(g) + O2(g), H = + 197kJ

2SO2(g) + O2(g)

Energy
products

H = + 197 kJ (heat absorbed)

2SO3(g)

H = H products – H reactants
reactants

Endothermic Reaction
 Exothermic processes Endothermic processes
making ice cubes melting ice cubes
formation of snow in clouds conversion of frost to water vapor

condensation of rain from water vapor evaporation of water

a candle flame forming a cation from an atom in the gas phase

mixing sodium sulfite and bleach baking bread

rusting iron cooking an egg
burning sugar producing sugar by photosynthesis
forming ion pairs separating ion pairs

combining atoms to make a molecule in splitting a gas molecule apart

the gas phase

mixing water and strong acids mixing water and ammonium nitrate
mixing water with an anhydrous salt making an anhydrous salt from a hydrate
crystallizing liquid salts (as in sodium melting solid salts
acetate in chemical handwarmers)

nuclear fission reaction of barium hydroxide octahydrate crystals

with dry ammonium chloride

mixing water with calcium chloride reaction of thionyl chloride (SOCl2) with cobalt(II)
sulfate heptahydrate
Exothermic VS Endothermic
Exothermic Reaction
Energy is released.
Energy is a product of the
Energy reaction.
absorbed or Reaction vessel becomes
released warmer.
Temperature inside reaction
vessel increases.
Relative Energy of the reactants is
Energy of greater
reactants & than the energy of the products
products H(reactants) > H(products)
H = H(products) - H(reactants)
Sign of H
= negative (-ve)
Endothermic Reaction
Energy is absorbed.
Energy is a reactant of the
reaction.
Reaction vessel becomes
cooler.
Temperature inside reaction
vessel decreases.
Energy of the reactants is less
than
the energy of the products
H(reactants) < H(products)
H = H(products) - H(reactants)
= positive (+ve)
 Sample Problem Drawing Enthalpy Diagrams and Determining
the Sign of ΔH
PROBLEM: In each of the following cases, determine the sign of ΔH, 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 ΔH = -285.8kJ ENDOTHERMIC ΔH = +40.7kJ

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

* 15
 Sample problem
(Drawing Enthalpy Diagrams and Determining
the sign of ΔH)
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.

* 16
* 17
 Activation Energy

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

* 18
 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.

* 19
 Activation Energy
(Reverse reaction)

* 20
Amount of heat that has been absorbed or released in a particular process
can be calculated by;

q = m x c x t

q = C x t

t = tfinal - tinitial

Simple calorimeter
21
CALORIMETER
Constant pressure calorimeter

qsys = qwater + qbomb + qrxn

qsys = 0 qbomb = 0

qrxn = - (qwater)

qwater = m x c x t

H = qrxn/n

Bomb calorimeter

No heat enters or leaves!

22
 Coffee-cup calorimeter.

* 23
 Measuring Energy Changes, ΔE
■ Using bomb calorimeter

■ Constant-Volume Calorimeter

■ At constant volume, qv

■ W = PΔV = 0
■ ΔE = q + w = qv + 0 =qv
■ So , ΔE = qv

* 24
 Figure 6.10

A bomb calorimeter

* 25
 BOMB CALORIMETER

■ For reactions involving gas

■ Higher temperature
■ -q reaction = +q calorimeter
■ q reaction = Ccal x ΔT (after bomb calorimeter
has been calibrated)

* 26
 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?
PLAN: - q sample = qcalorimeter

SOLUTION: qcalorimeter = heat capacity x ΔT

= 8.151 kJ/K x 4.937 K

= 40.24 kJ

40.24 kJ kcal = 9.63 kcal or Calories

4.18 kJ

The manufacturer’s claim is true.

* 27
 Measuring heat Changes

In general;
Heat (q) =
mass heated (g) x specific heat capacity (J g-1K-1) x
change in temperature (K)
or
q = m c ΔT
Unit = kJmol-1

* 28
 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.

* 29
Heat capacity and specific heat
■ The heat capacity, C is the amount of heat (Q)
required to raise the temperature of a given quantity
(m) of the substance by one degree Celsius. Units
J/˚C

■ The specific heat ,c @ s is the amount of heat (Q)

required to raise the temperature of one gram of the
substance by one degree Celsius. Units J/g.˚C

■ The molar heat capacity is the heat needed to

raise its temperature of one mol of the substance by
1oC. Units J/moloC

■ The specific heat of water is 4.18 J g-1 oC-1

■ The relation between the amount of heat (Q) and
specific heat (c) is given by
NOTE: if T in oC no need to
change to K

Q = heat absorbed
QQ= = mass
heat (g) x specific heat (c) x temperature
absorbed
change(∆t)
Q = mass (g) x specific heat (c) x temperature change(∆T)
= m.c.T
= m.c.T
specific heat (c) = Q
specific heat (c) = Q m. T
m. T

Heat capacity = mass x specific heat

C =mxc
Example:

Calculate the heat absorbed (Q) by 15.0 g of water to

raise its temperature from 20.0oC to 50.0oC. The specific
heat of water is 4.18 J/(goC).

Solution:
Note: no need to change to K
Q = mcT,

temperature change, T= 50oC – 20oC = 30oC, therefore

Q = mcT
= 15 g x 4.18 J/g.oC x 30oC = 1880 J or 1.88 kJ
Example:

How much heat is given off when an 869 g iron bar cools from 94oC to
5oC?

c of Fe = 0.444 J/g •oC

t = tfinal – tinitial = 5oC – 94oC = - 89oC

Q = mct

= 869 g x 0.444 J/g • oC x (–89oC) = - 34,000 J or 34 kJ

33
 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

* 34
 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.

* 35
 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
Note: metals have
Compounds relatively low values of c
and water has a very
high value,
water, H2O(l) 4.184
So water takes over 30
ethyl alcohol, C2H5OH(l) 2.46 times as much energy to
increase the temp of a
ethylene glycol, (CH2OH)2(l) 2.42 gram of water by 1K as
compared to a gram of
gold.
carbon tetrachloride, CCl4(l) 0.864

* 36
 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.

* 37
 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).

* 38
 Stoichiometry Of Thermochemical
Equations
CH4(g) + 2O2(g) → CO2(g) + 2H2O(l) ΔHrxn= -882kJ mol-1

■ A thermochemical equation is a balanced

equation that includes the heat of reaction, ΔHrxn.

■ ΔHrxn value shown refers to the amounts (moles)

of substances and their states of matter in that
specific equations.
* 39
 Stoichiometry Of Thermochemical
Equations
■ Sign.
The sign of ΔH depends on whether the
reaction is exothermic (-) or endothermic(+).
A forward reaction has the opposite sign of
the reverse reaction.

■ Magnitude.
The magnitude of ΔH is proportional to the
amount of substance reacting.

* 40
Types of Enthalpy Changes

Enthalpy of Combustion

is the heat released when 1 mole of a

substance is completely burnt in oxygen.

* 41
 Enthalpy of Combustion
thermochemical equation.
CH4(g) + 2O2(g) → CO2(g) + 2H2O(l) ΔH=-882kJ mol-1

CH3OH(l) + 1½O2(g) → CO2(g) + 2H2O(l) ΔH=-715kJ mol-1

C2H5OH(l) + 3O2(g) → 2CO2(g) + 3H2O(l) ΔH=-1371kJ mol-1

C3H7OH(l) + 4½O2(g) → 3CO2(g) + 4H2O(l) ΔH=-2010kJ mol-1

C4H9OH(l) + 6O2(g) → 4CO2(g) + 5H2O(l) ΔH=-2670kJ mol-1

* 42
Formula for calculation combustion reaction
1st formula

Heat liberated, Q = Heat absorbed by calorimeter + Heat absorbed by water

(absorbed
or released)
= CT mwatercT
m = mass water
C = heat capacity calorimeter c = specific heat capacity water
T = temperature change = 4.18 J/g K
T = temperature change

3rd formula 2nd formula

n = m
Hc = Q
Mr
n
m = mass of substance is
Q = heat liberated
burned
n = number of mol substance is burned
Mr = molar mass substance is
burned
Example:

A calorimeter has a heat capacity of 350 cal K-1 and

contains 880 g of water. 3.00 g of acetic acid, CH3COOH is
burned in excess oxygen in the calorimeter to give CO2 and
H2O and the temperature is observed to rise from 20.1 oC to
28.6oC.
Calculate the molar heat of combustion/ enthalpy change of
combustion of acetic acid.

Solution:
1. Q = mwatercwaterT + CcalorimeterT
2. norganic compound= m/RMM
3. Hc = Q / n
1. Q = mwaterc T + CT
= 880g(4.18) (28.6-20.1) J + ( 350 cal x 4.184 J) (28.6-20.1) J
= 31,2666.4 J + 12, 447.4 J
= 43713.8 J or 43.713 kJ

2. nacetic acid= m/RMM

= 3.00 g = 0.05 mol
60

3. H = Q/ n
= 43.713 kJ / 0.05 mol
= 874.26 kJ/mol
 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)

* 46
 Solution

Mass of water = 700 g

ΔT = final temp – initial temp = (38-35)°C = 13°C = 13 K
C = 4.2 Jg-1K-1
So , Q = cmΔT
= 4.2 Jg-1K-1 x 700g x 13 K
= 38 220 Joule
= 38.22 kJ
Mol ethanol was burned = 1.8 g / 46 gmol-1 = 0.039 mol

Thus, Heat of combustion of ethanol = Q / mol ethanol

= 38.22 kJ / 0.039 mol
= 980 kJmol-1

* 47
 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) ΔH=-40kJ mol-

1

NH4+NO3-(s) + (aq) → NH4+(aq) + NO3-(aq) ΔH=26kJ mol-1

* 48
 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) ΔH=-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.

* 49
 Sample Problem 6.4 Determining the Heat of a Reaction (H neut)

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
ΔHrxn (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
ΔT. The heat divided by the M of water will give us the heat per mole of
water formed.

* 50
 Sample Problem 6.4 Determining the Heat of a Reaction
continued

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

H+(aq) + OH-(aq) H2O(l)

For NaOH 0.500 M x 0.0500 L = 0.0250 mol OH-

For HCl 0.500 M x 0.0250 L = 0.0125 mol H+
HCl is the limiting reactant.
0.0125 mol of H2O will form during the rxn.
total volume after mixing = 0.0750 L

0.0750 L x 103 mL/L x 1.00 g/mL = 75.0 g of water

q = mass x specific heat x ΔT

= 75.0 g x 4.18 J/g*0C x (27.21-25.00)0C

= 693 J
(693 J/0.0125 mol H2O)(kJ/103 J) = 55.4 kJ/ mol H2O formed

* 51
Example
100 cm3 1.0 M HCl and 100 cm3 of 1.0 M NaOH
are mixed. Both solutions were originally at 24.6oC.
After the reaction has completed, the final
temperature is 31.3oC.
Calculate the enthalpy change for the neutralization
of HCl by NaOH. (Assume that the solution has a
density of 1 g/cm3 and specific heat capacity of 4.18
J/goC.
Solution
Heat released, q = mc∆T
= (100+100) x 4.18 x6.7
= 5601.2 J
Mol of NaOH = 1M x (100/1000) = 0.1 mol
Mol of HCl used = 1.0M x (100/1000) = 0.1 mol
HCl or NaOH is the limiting reactant (same mol)
LR < mol
0.1 mol of H2O will form during the rxn.

Enthalpy of neutralization = q/mol

= 5601.2/0.1
= 56012 J/mol
= 56.01 kJ/mol
 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).

* 54
 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) ΔH°= negative

Hence, energy is required to separate the ions :
NaCl (s) → Na+ (g) + Cl- (g) ΔH°= positive

The greater the lattice energy the higher the melting

point of the compound.

* 55
 Enthalpy of Formation

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) ΔH°f =-85kJ mol-1

2C(s) + H2(g) → C2H2(g) ΔH°f =+237kJ mol-1

* 56
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.

* 57
 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
ΔH0f.
(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) ΔH0f = -127.0 kJ

(b) Ca(s) + C(graphite) + 3/2O2(g) CaCO3(s) ΔH0f = -1206.9 kJ

(c) 1/2H2(g) + C(graphite) + 1/2N2(g) HCN(g) ΔH0f = 135 kJ

* 58
 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

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

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

* 59
 Some Important Types of Enthalpy Change

heat of combustion (ΔHcomb)

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

heat of formation (ΔHf)

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

heat of fusion (ΔHfus)

NaCl(s) NaCl(l)

heat of vaporization (ΔHvap)

C6H6(l) C6H6(g)

* 60
 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 ΔH which are impossible
to do in 1step, especially enthalpies of formation.

* 61
HESS LAW & CALCULATIONS

■ States that the heat of a reaction is

constant, whether the reaction is carried out
directly in one step or indirectly through a
number of steps with the initial and the final
states of the reaction remaining the same.

Hrxn = H1 + H2

■ The magnitude of the enthalpy change a chemical
reaction depends only on the different in the enthalpy
content of the products and the reactants, and does not
depend on how the reaction is completed.

■ This idea is state in Hess’ law.

■ Hess’ law state that the heat liberated or absorbed

during a chemical reaction is independent of the route
by which the chemical change occurs, provided the
initial and final conditions are the same
-cont: Hess Law
Reactants (A+B)

Route 2
Route 1

H1 H2
(intermediate)

H3

Products (C+D)
- The energy change in converting the reactants A+B to
the products C+D is the same, regardless of the route
taken.
- The energy diagram above summarises Hess’s law
H1= H2 + H3

where H1 refers to the direct route (route 1) and

(H2 + H3) refers to the indirect route (route 2)

- Such a diagram is often called an enthalpy cycle

 Using Hess’s Law to Determine
Enthalpies of Chemical Reactions

■ Using two methods:

(i) The Indirect Method (using thermochemical
equations) – Hess’ Law

(ii) The Direct Method (using standard of formation,

H0f )

H =  H0f (products) -  H0f (reactants)

 Refer exp 2: Determine the heat of formation of
magnesium oxide using Hess’ Law (Indirect Method)

- 1st exp : Mg + 2HCl  MgCl2 + H2 H2 (b)

- 2nd exp : MgO + 2HCl  MgCl2 + H2O H3 (c)

- H2 + ½ O2  H2O H4 (d)

Mg + ½ O2  MgO H1 (a)

1 mole product
- Mg + 2HCl  MgCl2 + H2 H2 (b)

2nd exp - reverse: +

- MgCl2 + H2O  MgO + 2HCl H3 (-c)
+
- H2 + ½ O2  H2O H4 (d)

Mg + ½ O2  MgO H1 (a)

 H1 = H2 + H3 + H4
x = b + (-c) + d
x = b–c+d
Example 1 :

Calculate the standard heat of formation of carbon

monoxide, given the standard enthalpy changes of
(i) combustion of carbon:
C(s) + O2(g) → CO2(g) Hf = -393 kJmol-1

(ii) standard enthalpy changes of combustion of

carbon monoxide:
CO(g) + ½ O2(g) → CO2(g) Hf = -283 kJmol-1
 1 mole product

C(s) + ½ O2(g) → CO(g) Hf ????

Using 2 equations: (combustion reaction)

(i) C(s) + O2(g) → CO2(g) Hc C = -393 kJmol-1

(ii) CO(g) + ½ O2(g) → CO2(g) Hc CO = -283 kJmol-1

 C(s) + O2(g) → CO2(g) Hf = -393 kJmol-1

reverse eq (ii) +
CO2(g) → CO(g) + ½ O2(g) Hf = +283 kJmol-1

C(s) + ½ O2(g) → CO(g) Hf = -110 kJmol-1

For O2(g) 1 – ½ = ½
Example 2:
Calculate the enthalpy of formation of liquid ethanol from the
following data.

C2H5OH(l) + 3O2(g)  2CO2(g) + 3H2O(l) H = -1367.8 kJ/mol........1

C(s) + O2(g)  CO2(g) H = -393.5 kJ/mol..........2
H2(g) + ½ O2(g)  H2O(l) H = -285.8 kJ/mol..........3

Solution:

Derive the equation formation of ethanol

2C + 3H2 + ½ O2  C2H5OH
Rearrange the equation:
For O2(g) (2 + 3 /2)- 3 = ½
Reverse equation 1
2CO2 + 3H2O  C2H5OH + 3O2 H = +1367.8
Equation 2 X 2: +
2C + 2O2  2CO2 H = 2(-393.5) = - 787
Equation 3 X 3 +
3H2+ 3/2 O2  3H2O H = 3(-285.8) = -857.4

 2C + 3H2 + ½ O2  C2H5OH

H =+1367.8 + (-787) + (-857.4)

= -276.6 kJ/mol
Eg: The Direct Method (using standard of formation, H0f )

■ The enthalpy of formation of an element in its standard state at

25 °C is zero. Eg Hf(Br2,O2,H2,C,Cr,= 0
■ The enthalpy of formation of H+ (aq) is also zero

Calculate the standard enthalpy of formation of C2H4O2(l)

Given: H0c of C2H4O2(l) = -876 kJ mol-1

H0c of H2(g) = -286 kJ mol-1 or H0f of H2O
H0c of C(s) = -396 kJ mol-1 or H0f of CO2
■ Solution

You must know how to write thermochemical equation

for the combustion of C2H4O2(l)

C2H4O2(l) + 2O2(g)  2CO2(g) + 2H2O(l) H0c -876 kJ mol-1

reactants products
Given: H0c of H2(g) = -286 kJ mol-1

H2 + ½ O2(g)  H2O(l) H0c H2(g) = -286 kJ mol-1

0r
1 mole 1 mole
reactant product H0f H2O(l) = -286 kJ mol-1

H 0c of C(s) = -396 kJ mol-1

C(s) + O2(g)  CO2(l) H0c C(s) = -396 kJ mol-1

0r
1 mole
reactant
1 mole
product
H0f CO2(l) = -396 kJ mol-1
■ Using formula
H =  H0f (products) -  H0f (reactants)

???
C2H4O2(l) + 2O2(g)  2CO2(g) + 2H2O(l) H0c -876 kJ mol1

reactants products H0f O2(l)= 0

-876 kJ mol1 = 2(-396 kJ mol-1) + 2(-286 kJ mol-1) - x +0

= -1364 - x
-x = 488 kJ mol-1
 x = - 488 kJ mol-1
x = standard enthalpy of formation of C2H4O2(l)
2C + 2H2 + O2  C2H4O2
H0f C2H4O2 = -488 kJ mol-1
Standard Heats Of Reaction, ΔH°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)

ΔH = ∑H products – ∑H reactants

* 79
 Sample Problem

■ Use the following information to find ΔH°f of

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

ΔH°f of CO2(g) = - 393.5 kJmol-1

ΔH°f of H2O(g) = - 241.8 kJmol-1

(answer: -238.6 kJ)

* 80
 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)

ΔHrxn (kJ/mol) gained or lost

* 81
 Figure 6.13

The general process for determining ΔH0rxn from ΔH0f values.

Elements

decomposition
Enthalpy, H

-ΔH0f ΔH0f

formation
Reactants
Hinitial

ΔH0rxn

Products
Hfinal

ΔH0rxn = Σ mΔH0f(products) - Σ nΔH0f(reactants)

* 82
 Table 6.5 Selected Standard Heats of Formation at 250C(298K)

Formula ΔH0f(kJ/mol) Formula ΔH0f(kJ/mol) Formula ΔH0f(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
* 83
 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 ΔH0rxn from ΔH0f values.

PLAN: Look up the ΔH0f values and use Hess’s Law to find ΔHrxn.

SOLUTION: ΔHrxn = Σ mΔH0f (products) - Σ nΔH0f (reactants)

ΔHrxn = [4(ΔH0f NO(g) + 6(ΔH0f H2O(g)] - [4(ΔH0f NH3(g) + 5(ΔH0f 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)]

ΔHrxn = -906 kJ

* 84
 EXAMPLE FINAL CHM431 MAC 2014
A dilute solution of hydrochloric acid with a mass of 610.3 g and
containing 0.3 mol of HCl was exactly neutralized in a calorimeter by
615.3 g sodium hydroxide of a comparably dilute solution. The
temperature increased from 16.7 to 20.6 oC. The specific heat of the
hydrochloric acid and sodium hydroxide solution was 4.031 J g-1 oC-1
and 4.046 J g-1 oC-1, respectively. The heat capacity of the calorimeter
was 77.99 J oC-1. Use this data to calculate the heat of reaction, which
occurs by the following equation:

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

Assume that the original solutions made independent contributions to

the total heat capacity of the system following their mixing.
(5 marks)

* 85
 q = mC∆T + C∆T
= [mHCl C∆T+ mNaOHC∆T] + Ccal∆T
=[(610.29gx4.031J/goCx3.8)+ (1 mark)
(615.31gx4.031J/goCx3.8oC)]+(1 mark)
77.99J/oCx3.8oC (1 mark)
= 18937 J @ 18.9 kJ

0.3318 mol HCl -----18.9 kJ

1 mol HCl -----(1/0.3318) x 18 9 kJ
= 57.1 kJ (2 marks)

* 86
 GET IT DONE!!!!

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