THERMOCHEMISTY

EB 3108-CHAPTER 3
Rashmirekha Sahoo

Thermo chemistry
Thermodynamics is the science of heat
(energy) transfer.

Heat energy is associated with

molecular motions. the study of heat
Heat transfers until thermal equilibrium
is established.

chang e
in chemical
reactions

Energy & Chemistry

Energy is the capacity to do work or
transfer heat.(
heat.(Chemist define work as
directed energy change resulting from a
process)

Heat is the form of energy that flows

between 2 objects because of their
difference in temperature
temperature..
Other forms of energy

light
electrical
kinetic and potential

Internal Energy (E)

PE + KE = Internal energy (E or U)
Int. E of a chemical system depends on
number of particles
type of particles
temperature

Potential energy
Potential energy of a motionless
body has by virtue of its position.
Positive and
negative
particles (ions)
attract one
another.

Energy and Its Units

Kinetic energy is the energy associated with an object by
virtue of its motion.
Ek = mv2

rotate
vibrate
translate

1 calorie = heat required to raise temp. of

1.00 g of H2O by 1.0 oC.
1000 cal = 1 kilocalorie = 1 kcal
1 kcal = 1 Calorie (a food calorie)
(What you'll find on food packaging, calories = kilocalories and are used
interchangeably)

But we use the unit called the JOULE

1 cal = 4.184 J
6

Energy Change in Chemical

Processes
The total energy is
unchanged in a chemical
reaction.(law of
coservation of energy)
If PE of products less than
reactants, the difference
must be released as KE.

PE
Reactants
Kinetic
Energy

Products

PE of system dropped. KE increased. Therefore, you often

feel a T increase.

In the system below, the water could have reached room

temperature from either direction.
Therefore, internal energy is a state function.
It depends only on the present state of the system, not on
the path by which the system arrived at that state.
And so, E depends only on Einitial and Efinal.

Heat of Reaction
Heat (denoted q) is the energy that flows into or out
of a system because of a difference in temperature
between the thermodynamic system and its
surroundings.
The heat of reaction (at a given temperature) is the
value of q required to return a system to the given
temperature at the completion of the reaction

 An exothermic process is a chemical reaction or a physical

change in which heat is evolved (q is negative) or is a process
that gives off heat transfers thermal energy from the system
to the surrounding.

2H2 (g) + O2 (g)

2H2O (l) + energy

An endothermic process is a chemical reaction or a physical

change in which heat is absorbed (q is positive) or is a
process in which heat has to be supplied to the system from
the surroundings.
energy + 2HgO (s)

2Hg (l) + O2 (g)

Enthalpy (H) is used to quantify the heat flow into or out of a system in a
process that occurs at constant pressure

H = heat given off or absorbed during a reaction at constant pressure

H = H (products) H (reactants)

Hproducts < Hreactants

H < 0

Hproducts > Hreactants

H > 0
6.3

Enthalpy is a state function.

Enthalpy is the internal energy plus the product of
pressure and volume:

H = E + PV
A state function is a property of a system that depends
only on its present state, which is determined by
variables such as temperature and pressure, and is
independent of any previous history of the system.

Enthalpy of Reaction
The enthalpy of reaction, H, is the difference between the
enthalpies of the products and the enthalpies of the
reactants:

H = H (products) H (reactants)
The enthalpy of reaction equals the heat of reaction at
constant pressure.

H = qp

2.Thermochemical Equations
A thermochemical equation is the chemical equation for a
reaction (including phase labels) in which the equation is
given a molar interpretation, and the enthalpy of reaction
for these molar amounts is written directly after the
equation.
E.g.
2Na(s) + 2H2O(l) 2NaOH (aq) + H2(g)
H = 367.5 kJ

Thermochemical Equations
Is H negative or positive?
System absorbs heat
Endothermic
H > 0

6.01 kJ are absorbed for every 1 mole of ice that melts at

00C and 1 atm.
H = 6.01 kJ
H2O (s)
H2O (l)
6.3

Thermochemical Equations
Is H negative or positive?
System gives off heat
Exothermic
H < 0

890.4 kJ are released for every 1 mole of methane that is

combusted at 250C and 1 atm.
CH4 (g) + 2O2 (g)
CO2 (g) + 2H2O (l) H = -890.4 kJ
6.3

Thermochemical Equations

The physical states of all reactants and products must be

specified in thermochemical equations.
2H2(g) + O2 (g) 2H2O (g)
H = 483.7 kJ
2H2 (g) + O2 (g) 2H2O (l)
H = 571.7 kJ
(Additional heat is released when water vapour condenses to liquid )

How much heat is evolved when 266 g of white phosphorus

(P4) burn in air?
P4 (s) + 5O2 (g)
P4O10 (s) H = -3013 kJ
266 g P4 x

1 mol P4
123.9 g P4

3013 kJ
= -6470 kJ
x
1 mol P4

6.3

A typical chemical equation is S + O2 SO2

It is called a thermochemical equation when we add
information about H
S + O2 SO2 H = 296.9 kJ
If we change the equation, then the H also changes
SO2 S + O2 H = + 296.9 kJ
If the reaction is reversed the sign is reversed
Also, if numbers in the equation change, so will the
amount of energy produced/absorbed:
2S + 2O2 2SO2 H = 593.8 kJ

Exercise
1) A propellant for rockets is obtained by mixing the liquids
hydrazine, N2H4, and dinitrogen tetroxide, N2O4. These
compounds react to give gaseous nigrogen, N2, and water
vapour, evolving 1049 kJ of heat at constant pressure
when 1 mol N2O4 reacts.
Write the thermochemical equation for this reaction.

Exercise (contd)
2 (a)

Write the thermochemical equation for the

reaction described in the above Exercise for the case
involving 1 mol N2H4 .
(b) Write the thermochemical equation for the reverse of
the reaction described
in the previous Exercise.

Exercise (contd)
3. How much heat evolves when
10.0 g of hydrazine reacts
according to the reaction
described in Question 1?

3.Measuring Heats of Reaction

The specific heat (s) of a sample of substance is the quantity of heat
(q)needed to raise the temperature of one gram of substance by one
degree Celsius.
Heat (q) absorbed or released

The heat capacity (C) of a substance is the amount of heat (q) required to
raise the temperature of a given quantity (m) of the substance by one degree
Celsius

Heat capacity ,C = ms
The mass, m (in grams) is, heat q, required to raise the
temperature of a sample OR q = Ct
q = s x m x t

(t = tfinal tinitial)

Specific Heats and Molar Heat Capacities of Some

Substances (at 25oC)
______________________________________
Substance Specific Heat
Molar Heat Capacity
J/(mol.oC)
J/(g.oC)
______________________________________
Aluminium, Al
0.901
24.3
Copper, Cu
0.384
24.4
Ethanol, C2H5OH
2.43
112.0
Iron, Fe
0.449
25.1
4.18
75.3
Water, H2O

How much heat is given off when an 869 g iron bar cools from
940C to 50C?
s of Fe = 0.444 J/g 0C
t = tfinal tinitial = 50C 940C = -890C
q = mst = 869 g x 0.444 J/g 0C x 890C

= -34,000 J

6.4

Exercise
Iron metal has a specific heat of 0.449 J/ (g.oC). How much
heat is transferred to a 5.00 g piece of iron, initially at
20.0oC, when it is placed in a pot of boiling water? Assume
that the temperature of the water is 100.0oC and that the
water remains at this temperature, which is the final
temperature of the iron.

Heat & Changes of State

How much heat is required to raise the
temperature of 500. g water to steam at 100 oC?
2. To raise water from 0 oC to 100 oC
q = (500. g)(4.2 J/
J/gC
gC)(
)(100
100 - 0) 0C = 2.1 x 105 J

Hesss Law
Hesss law of heat summation states that for a
chemical equation that can be written as the sum of two or
more steps, the enthalpy change for the overall equation
equals the sum of the enthalpy changes for the individual
steps. OR
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

For example, to find the enthalpy change for the

combustion of graphite to carbon monoxide
2 C (graphite) + O2 (g) 2 CO (g)

 Imagine that the reaction takes place in two

separate steps:
2 C (graphite) + 2 O2 (g) 2 CO2 (g)
2 CO2 (g) 2 CO (g) + O2 (g)
Given:
2 C (graphite) + 2 O2 (g) 2 CO2 (g)
2 CO (g) + O2 (g) 2 CO2 (g)

H = ( 393.5 kJ) x 2
H = 566.0 kJ

2 C (graphite) + 2 O2 (g) 2 CO2 (g) H1 = ( 393.5 kJ) x 2

2 CO2 (g) 2 CO (g) + O2 (g)
H2 = + 566.0 kJ
---2 C (graphite) + O2 (g) 2 CO (g) H3 = 221.0 kJ
2

Exercise
Manganese metal can be obtained by reaction of
manganese dioxide with aluminium.
4 Al (s) + 3 MnO2 (s) 2 Al2 O3 (s) + 3 Mn (s)
What is H for this reaction? Use the following data:
2 Al (s) + 3/2 O2 (g) Al2 O3 (s)
Mn (s) + O2 (g) Mn O2 (s)

H = 1676 kJ
H = 521kJ

Practice

Given:
CH4(g) C(s) + 2H2(g); H = 74.6 kJ/mol
C(s) + O2(g) CO2(g); H = -393.5 kJ/mol
H2(g) + 1/2O2(g) H2O(g); H= -241.8 kJ/mol

CH4(g) + 2O2(g) CO2(g) + 2H2O(g); Htot = ?

Standard Enthalpies of Formation

Definitions
The term standard state refers to the standard

thermodynamic conditions chosen for substances when

listing or comparing thermodynamic data: 1 atm pressure
and the specified temperature (usually 25oC).

An allotrope is one of two or more distinct forms of

an element in the same physical state, e.g. carbon
and diamond.

Definitions (contd)

The reference form of an element is the stablest form (physical state and
allotrope) of the element under standard thermodynamic conditions. The
reference form of oxygen at 25oC is O2(g); the reference form of carbon at
25oC is graphite.

The standard enthalpy of formation of a substance, denoted

Hfo, is the enthalpy change that results when one mole of a compound
is formed from its elements at a pressure of 1 atm (in its standard state).
The standard enthalpy of formation of any element in its most stable
form is zero
H0 (O2) = 0

H0 (C, graphite) = 0

For example: C (graphite) C (diamond)

Hfo = 1.9 kJ.

3

6.5

 Ho = nHfo (products) - m Hfo (reactants)

The stanard enthalpy of reaction
o

H f = H

o
final

o
initial

= ni H ( products ) n j H ( reactants )
o
f

o
f

Consider the equation:

CH4 (g) + 4Cl2 (g) CCl4 (l) + 4 HCl (g)
Ho = [Hfo (CCl4 ) + 4 Hfo (HCl)] [Hfo (CH4 ) + 4 Hfo (Cl2)]
= [( 139) + 4 (92.3)] kJ [(74.9) + 4 (0)] kJ
= 433 kJ.

Calculation of H
C3H8 (g) + 5 O2 (g) 3 CO2 (g) + 4 H2O (l)

H = [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

The Truth about Enthalpy

1.Enthalpy is an extensive property.
2. H for a reaction in the forward direction is

equal in size, but opposite in sign, to H for the

reverse reaction.
3. H for a reaction depends on the state of the
products and the state of the reactants.

Calorimetry
Since we cannot know the exact enthalpy of the
reactants and products, we measure H through

calorimetry, the measurement of heat flow.

Calorimetry
Some heat from reaction warms water
qwater = (sp. ht.)(water mass)(T)

Some heat from reaction warms

bomb
qbomb = (heat capacity, J/K)(T)

Total heat evolved = qtotal = qwater + qbomb

Measuring Heats of Reaction

CALORIMETRY
Calculate heat of combustion of octane.
C8H18 + 25/2 O2 --->
> 8 CO2 + 9 H2O
Burn 1.00 g of octane
Temp rises from 25.00 to 33.20 oC
Calorimeter contains 1200 g water
Heat capacity of bomb = 837 J/K

Measuring Heats of Reaction

CALORIMETRY
Step 1-Calc. heat transferred from reaction to water.
q = (4.184 J/gK)(1200 g)(8.20 K) = 41,170 J
Step 2-Calc. heat transferred from reaction to bomb.
q = (bomb heat capacity)(T)
= (837 J/K)(8.20 K) = 6860 J
Step 3-Total heat evolved
41,170 J + 6860 J = 48,030 J
Heat of combustion of 1.00 g of octane = - 48.0 kJ