TOPIC 2:

T HERMODYNAMICS (PART I)

2 LEARNING OBJECTIVE:

 Understand 1st law of thermodynamics.

 Define specific heat capacity and calculate the
amount of heat change in a calorimeter.
 Apply Hess law to find enthalpy change of a
chemical reaction.
 Use standard enthalpy change of formation data
to calculate enthalpy change of a chemical
reaction.
3 INTRODUCTION

 Energy is the capacity to do work or to

produce heat.
 In thermochemistry, the universe is defined
as system + surroundings.
 System is the reaction or process being
studied.
 Surrounding is everything else in the
universe except the system.
4
F IRST L AW OF T HERMODYNAMIC

 Can be stated in terms of:

 Law of conservation of energy
Energy can neither be created nor
destroyed but it can be converted from
one form to another.
 Energy, work & heat
The change in the internal energy of a
system is the sum of the energy it gains
as heat plus the energy it gains from
having work done on it.
 5 Energy, work & heat
Internal Energy
Sum of kinetic and
potential energies of all
particles in the system

U = q - W

Where,
U = Change in systems
internal energy
q = Actual heat change
w = work done by the
system
6
Reactions carried out at
different conditions
 Reactions carried out at constant volume,
V = 0, since w = PV = 0,
qv = U
 Reactions carried out at constant pressure,
qp = (Ufinal Uinitial) + P(Vfinal Vinitial)
Rearrange:
qp = (Ufinal + PVfinal) (Uinitial + PVinitial)
= Hfinal Hinitial
= H (Enthalpy/ heat content)

Therefore: qp = H = U + W
7
C ONSTANT-P
C ALORIMETRY

At constant P,
heat released by reaction =
heat absorbed by calorimeter + heat
absorbed by solution

A C OFFEE -C UP C ALORIMETER
M ADE OF T WO S TYROFOAM C UPS
THERMODYNAMICS & EQUILIBRIUM MARCH 2008
8 C ONSTANT -V CALORIMETRY

THERMODYNAMICS & EQUILIBRIUM

A Bomb Calorimeter
9 U & H IN COMPARISON

 In either case i.e. qp and qv can be measured by

measuring a change in T (assuming we know heat
capacities, check slide 16 to 26).
 Its easy to understand that for reaction involving
const. V, qv = U since no work has been done by the
system.
 For reaction involving const. P, PV term due to
volume expansion or compression.
 For solids and liquids (condensed phases), PV
contribution is small, and therefore qp H U
 For systems involving gases, H and U differs
significantly. W must be determined carefully.
Or dont measure qv, measure qp instead.
10
HEAT CHANGE IN
CHEMICAL REACTION

 All chemical substances have chemical

potential energy.
 In a chemical reaction, chemical potential
energy of substance is released or absorbed
as heat.
 If heat is released from system 
exothermic reaction.(H = ve)
 If heat is absorbed by the system 
endothermic reaction. (H = +ve)
 H EAT C HANGE IN
C HEMICAL R EACTION

Cold pack is applied to a

strain or sprain to relieves the
A soldier insert a hot pack in
pain
his clothes to keep him warm
during winter.
12 H OW A COLD PACK WORKS ?

 Cold pack contains a soluble salt like

ammonium nitrate.
 When the cold pack is squeezed, the solid salt
is mixed with water in the outer layers
27 kJ + NH4NO3(s)  NH4+(aq) + NO3(aq)
 Heat flows from the injured knee (part of
surroundings) into the cold pack (the system).
13 H OW A HOT PACK WORKS ?

 One type of hot pack contains fine iron

particles. These packs are kept in a sealed
container and release heat when they are
exposed to air.
 When the plastic wrap is removed, oxygen
from the air enter the pack. The oxygen
reacts with iron in the pack in an exothermic
reaction:
 4Fe(s) + 3O2(g)  2Fe2O3 (s) + 1625 kJ
14 H OW A HOT PACK WORKS ?

 Heat produced by the reaction flows from

the hot pack (system) to your body(part of
the surroundings).
 As system (hot pack) loses heat to the
surrounding, this is an exothermic reaction.
 15 E NTHALPY DIAGRAMS

4Fe(s) + 3O2(g)
Enthalpy

Enthalpy
reactants NH4+(aq) + NO3-(aq)
H = -1625 kJ products
H = +27 kJ

2Fe2O3(s) NH4NO3(s)
products reactants
(a) Exothermic reaction (b) Endothermic reaction
H<0 H>0

Figure 1: Enthalpy diagrams of (a) exothermic reaction (b) endothermic reaction

MEASURING ENTHALPY
CHANGE: CALORIMETRY


17
M EASURING H EAT C HANGE USING
CALORIMETER

 Calorimeter is an insulated device used for

measuring the amount of heat released or absorbed
during a chemical or physical process.
 Usually a known mass of water, m with known
specific heat capacity, c, is placed in an insulated
device to absorb heat released, Q from the chemical
process and the difference in temperature is
measured, T.
Q = m c T
18 HEAT CAPACITY

 Same amount of heat do not give the same

temperature changes in two different
substances.
 Specific heat capacity: amount of heat required
to raise the temperature of 1 gram of that
substance by 10 Kelvin.
 Molar heat capacity: amount of heat required
to raise the temperature of 1 mol of a substance
by 10 Kelvin
19 EXAMPLES
Table 1: Specific heat and molar heat capacities for some common substances.

Substance Specific Heat Capacity Molar Heat Capacity

( J. g 1. K 1 ) ( J. mol 1. K 1 )

Copper (s) 0.385 24.5

Aluminum (s) 0.900 24.3

Iron (s) 0.450 25.1

H2O(l) 4.18 75.3

H2O(g) 2.03 36.4

 EXAMPLE1:
20 DETERMINE SPECIFIC HEAT
CAPACITY
 Suppose you put 125 g of water into a foam-cup calorimeter
and find that its initial temperature is 25.60C.
 Then you heat a 50.0 g sample of an unknown metal to a
temperature of 115.0 0C and put the metal to the cooler
water and the temperature of the water rises.
 The flow of heat stops only when the temperature of the
metal and the water are equal, which is 29.30C.
 Assuming no heat is lost to surroundings, the heat gained by
water is equal to the heat loss by the metal. What is the
specific heat of the unknown metal?
21 E XAMPLE 1 S OLUTION :

 Heat absorbed by water,

Qwater = 125 g 4.18 J ( g .0 C ) ( 29.30 C 25 .6 0 C )
= 1930 J
 Heat lost by metal + Heat absorbed by water = 0 (conserved)
Qmetal = 50.0 g cmetal (29.3o C 115.0o C)
(50.0 g cmetal 85.7 o C) + 1930 J = 0 J
1930 J
cmetal =
(50.0 g )(85.7 o C)
= 0.450 J ( g.o C) 1 The metal is iron!
22 THINK CRITICALLY

 One lawn chair is made of aluminium and

another is made of iron. Both chairs are
painted the same colour.
 Given specific heat capacity of aluminium
and iron are 0.897 J/g.0C and 0.449 J/g.0C
respectively.
 On a sunny day, which chair will be hottest
to sit in? Explain why.
23
E XAMPLE 2:
C ALCULATE HEAT CHANGE
 Suppose an architect designs a house that is
to be partially heated by solar energy.
 A pond made of 14 500 kg of granite rock and
contain 22 500 kg of water used to absorb
heat from sun during day and harnessed for
use in the home.
 Calculate how much energy, in J actually solar
cell actually absorbed during the daylight
hours.
24
WHAT INFORMATION
NEEDED?

Given:
 Mass of granite rock = 14 500 kg
 Mass of water = 22 500 kg
Missing information:
 Specific heat capacity of granite rock and
water.
 Temperature change of granite rock and
water.
25
WHAT INFORMATION
NEEDED?

 After conducting experiments, the

architect finds that the temperature of the
water and granite increases an average of
220C during the daylight and decrease the
same amount during the night.
 Specific heat capacity of water is 4.184
J/(g.0C) and granite is 0.803 J/(g.0C) were
found in data book.
26 E XAMPLE 2 S OLUTION :
 Q = m x c x T
 For water, heat energy absorbed,
Qwater = 2.25 107 g 4.184 J /( g .0 C ) 220 C
= 2.1109 J
 For granite, heat energy absorbed,

Qgranite = 1.45 107 g 0.803J /( g.0 C ) 220 C

= 2.6 108 J
 Total energy absorbed = 2.4 x 109 J.
HESSS LAW AND ENTHALPY
CHANGE
28 HESSS LAW

 It is sometime difficult to measure enthalpy

change of reaction directly using
calorimetric method.
 Hesss Law is useful is such a case.
The total change for a chemical reaction is
independent of the path by which the
reaction occurs, provided the starting and
finishing states are the same for the reaction
path.
HESSS LAW
30 HESSS LAW

 There are two ways to use Hesss Law to

determine enthalpy change of a reaction.
 Summation of equations with known H;
 Standard enthalpy of formation data
Hf0(products) - nHf0(reactants)
n
31 Summation of Equations

 A series of equations with known enthalpy

change values must be given.
 The equations are rearranged in few ways:
 if the equation is multiplied with a factor, H is also
multiplied with the same factor.
 if the equation is reversed, the sign of H is reversed.
 Then the equations are summed up to form a new
equation.
 Enthalpy change of new equation is equal to
summation of all enthalpy changes.
32 EXAMPLE 3:

 Suppose you are studying the formation of

acid that results from the reaction of water in
the atmosphere with sulfur trioxide expelled
during a volcanic eruption.
 You need to determine the H for this
reaction:
2S(s) + 3O2(g)  2SO3(g) H = ?
33 BUT
 Unfortunately when you try to duplicate the
reaction in the laboratory by burning sulfur in
air, only small quantities of sulfur trioxide are
formed. The mixture obtained mostly sulfur
dioxide.
S(s) + O2(g)  SO2(g) H = -297 kJ
 From data book, we know that
2SO3(g)  2SO2(g) + O2(g) H = 198 kJ
 34 A PPLYING H ESS S L AW

2S(s) + 3O2(g)  2SO3(g) H = ?

(1) S(s) + O2(g)  SO2(g) H = -297 kJ
(2) 2SO3(g)  2SO2(g) + O2(g) H = 198 kJ

(1) 2S(s) + 2O2(g)  2SO2(g) H1 = -594 kJ

(2) 2SO2(g) + O2(g) 2SO3(g) H2 = -198 kJ
-------------------------------------------------
2S(s) + 3O2(g)  2SO3(g) H1+2= -792 kJ
35
S TANDARD E NTHALPY OF
F ORMATION
 Heat change when one mole of compound is
formed from its elements.
 For instance,
 S(s) + 3/2 O2(g)  SO3(g) H =-396 kJ
 N2(g) + O2(g)  NO2(g) H = +33.2 kJ
 O2(g)  O2(g) H = 0 kJ (no reaction)
(O2 is an element)
 CALCULATE H USING
H 0 F DATA
Definition:
Standard enthalpy of formation (H0f) is the
enthalpy change when 1 mol of the
compound is formed from the elements in
their standard states (at 298 K and 101.325
kPa i.e. 25C and 1 atm, can be solid, liquid or
gas).

Standard state Standard Temperature

and Pressure (STP) for a gas.
37
EXAMPLE 4:

 Calculate the Hreaction of the following

reaction:
H2S(g) + 4F2(g)  2HF(g) + SF6(g)
 Given the standard enthalpies of formation
for
 HF(g) : -273 kJ
 SF6(g) : -1220 kJ
 H2S(g): -21 kJ
38 E XAMPLE 4 S OLUTION :

H2S(g) + 4F2(g)  2HF(g) + SF6(g)

H = nHf(products) - nHf (reactants)

H = [2(HfHF)+ 1(HfSF6)]- [(HfH2S) +(HfF2)]

= [(2x-273) + (-1220)] [(-21) + (4x 0)]

= 1745 kJ
39
E XAMPLE 4 S OLUTION :
ALTERNATIVE
 Translate Hf0 into equations:
 Formation of HF(g):
1. H2(g) + F2(g)  HF(g) Hf = 273 kJ
2. S(s) + 3F2(g)  SF6(g) Hf = 1220 kJ
3. H2(g) + S(s)  H2S(g) Hf = 21 kJ
4. F2(g)  F2(g) Hf = 0
(F2 is an element)
  H2S(g) + 4F2(g)  2HF(g) + SF6(g), H = ?
40
 Rearrange the equations
 Multiply Equation (1) by 2:
H2(g) + F2(g)  2HF(g) H1 = -546 kJ

 Maintain Equation (2):

S(s) + 3F2(g)  SF6(g) H2 =-1220 kJ

 Reverse Equation (3)

H2S (g)  H2 (g) + S(s) H3 = +21 kJ

 Multiply Equation (4) by 4:

4F2 (g)  4F2 (g) H4 = 0
  Cancel common species on both sides of
41
equation.
H2(g) + F2(g)  2HF(g) H1 = -546 kJ

S(s) + 3F2(g)  SF6(g) H2 =-1220 kJ

H2S (g)  H2 (g) + S(s) H3 = +21 kJ

4F2 (g)  4F2 (g) H4 = 0

 Sum up the equation:
4F2(g) + H2S(g)  2HF(g) + SF6(g)

 Sum up the H:
H = H1 + H2 + H3 + H4 =
1745 kJ
 42

For thermite reaction:

Fe2O3(s) + 2Al(s) Al2O3(s) + 2Fe(s) Hrxn = ??? kJ mol-1
Given: Hf Fe2O3(s) = 826 kJ/mol
Hf Al2O3(s) = 1676 kJ/mol
Calculate H of the thermite reaction. Is the reaction
endothermic or exothermic in nature?
43 S UMMARY:

 To find enthalpy change of a reaction, H

 Calorimetric method:

Q = m c (Tfinal-Tinitial)
 Hesss Law of heat summation:
 Summation of few equations
 Standard enthalpy of formation
 Hf0(products) - Hf0(reactants)