Thermochemistry

Terminology 2

Thermochemistry:-
The branch of chemistry which deals with the
study of heat changes during a chemical
reaction is called theremochemsitry.
Heat of reaction
The amount of heat evolved or absorbed by a
chemical reaction at constant temperature
and pressure is called heat of reaction.
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Terminology 3

Temperature
The measure of average kinetic energy of
all particles of a system is called
temperature.
 Heat
The transfer of energy caused by the
difference of temperature between two
objects is called heat. 6/25/19
Termonology 4

Specific heat capacity

The amount of energy required to raise the
temperature of one kilogram of the substance by one
Kelvin.
Specific heat of water 4.184 kJ kg-1K-1
Calorie
The amount of energy required to raise the
temperature of one gram of water from 14.5 ºC to
15.5 ºC is called one calorie.
1000 cal = 1k cal 6/25/19
 Terminology 5

Newton
Newton is that force which produce the acceleration
of 1m s-2 in a body of 1kgS
1N = kg m s-2
1J = kg m s-2 m
1J = ( kg m2 s-2)
OR
“The kinetic energy possessed by an object with a mass
of 2kg traveling at 1 m/s.”
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Exothermic reactions 6

 Those reactions in which heat is evolved from

system to the surroundings are called as exothermic
reactions.
C(s) + O2(g)  CO2(g) ΔH = - 393.7 kJ mol-1
-ve sign shows that heat is released.
In exothermic reactions, the energy of reactants is
greater than products, so the reaction goes down the
hill, and extra energy is evolved to the surrounding.
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 Endothermic reactions 7

•Those reactions in which heat is absorbed from

surroundings to system are called endothermic
reactions.
• N2(g) + O2(g)  2NO(g) ΔH = + 180.5 kJ mol-1
•+ve sign shows that heat is absorbed.
In an exothermic reaction, the total heat contents of
the reactants are less than the products. So, the
reaction goes up the hill, and extra energy is
required to bring that change.
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 Spontaneous reactions 8

A process or reaction which takes place on

its own, without any outside assistance and
move from a non-equilibrium state towards an
equilibrium state is termed as spontaneous
Process: any physical change is called process.
Reaction: any chemical change is called reaction.

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Spontaneous Reaction (Examples) 9

1. Water flows from higher to lower level

2. Gas molecules move from a region of high
pressure to a region of low pressure.
3. Heat flows from hot to a cold body.
4. Neutralization of a strong acid with a strong base
NaOH(aq) + HCl(aq)  NaCl(aq) + H2O(l)
5. Disappearance of blue colour by adding Zn to
CuSO4
(Redox reaction: Transfer of charges) 6/25/19

Zn + CuSO4  ZnSO4 + Cu
Non spontaneous reactions 10

Non spontaneous process is the reverse of the

spontaneous process it does not take place on its own and
take place with external assistance
They do not occur in nature.
Examples
1. Pumping of water uphill
2. Transfer of heat from cold interior part of refrigerator
to hot surroundings.
3. Reaction of N2 and O2 to form NO by electric
discharge 6/25/19

N2(g) + O2(g)  2NO(g)

Terminology 11

System
The substance or mixture of substances
which is under experiment or under
consideration is called system.
Surroundings
Everything which is not a part of the
system is called surroundings
Boundary
The real or imaginary surface separating
the system from surrounding is called
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boundary.
Terminology 12

State of system
The condition of a system like temperature,
pressure, volume, enthalpy etc. is called state of
a system.
Initial state
The initial condition of system is called initial
state.
Final state
The condition of system during or after change is
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called final state.

Terminology 13

:Chang in State :-
The difference between final state
function and initial state function is called
change in state function
Δ E = E2 – E1
Δ E = Change in internal energy
E2 = Final state of energy
E1 = Initial state of energy 6/25/19
STATE FUNCTION:- 14

“A property that depends only on initial and

final states and is independent of the path
followed by the change is called state function”.
By convention, capital letters are used as symbols for a state
function.
1. Pressure (P)
2. Temperature (T)
3. Volume (V)
4. Internal energy (E)
5. Enthalpy (H) 6/25/19
Internal Energy:- 15

“The sum of all kinds of K.E and

P.E possessed by the molecules
or ions in the system is called
internal energy.”
E = K.E + P.E
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Kinetic Energy: 16

Kinetic energy is defined as energy of the

molecules due to motion.
• Motions of the molecules are of three types
• Translational
• Vibrational
• Rotational
• So the total K.E will be the sum of the K.E due to
these types of motions
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• K.E = E Translational + E Vibrational + E Rotational
Potential Energy: 17

P.E is defined as energy of the molecules

due to their arrangements.
• The absolute value of internal energy cannot be
determined. However, change in internal energy
can be measured.
Δ E = E2 – E1
 Dependence:-
Internal energy depends upon the motion,
molecular forces of attraction.
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 TRANSFER OF HEAT 18

There are two fundamental ways of transferring

energy to or from a system
Heat:
It is defined as the quantity of energy that flows across the boundary
of a system during a change due to difference in temperature between the
system and the surroundings.
It is not a state function. It is represented by a symbol q.
Work:-
It is defined as the product of force and distance.
W=FxS 6/25/19
W = Force x displacement
Units in SI system = Joules
 First law of thermodynamics 19

Energy can neither be created nor

destroyed, but can be changed from
one form to another
OR
Energy of universe remains constant
∆E = E2 -E1 = q+w
∆E = q - P∆V (Work is done by the system)
qp>qv At Constant volume
∆E = qv
(Enthalpy change)
∆H = ∆E + ∆(PV)
∆H = ∆E + P∆V 6/25/19
At Constant Pressure
∆H = qp
 Standard enthalpy of reaction 20
• The amount of energy
released or absorbed
when one certain
number of mole of the
reactant as indicated in
the balanced chemical
equation react together
to give products under
standard conditions

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2H2(g)+ O2(g) →2 H2O(l)∆Ho = -285.8kJmol-1
Standard Enthalpy of Formation (ΔHºf) 21

The standard enthalpy of formation is defined

as amount of heat evolved or absorbed when
mole of a substance is formed from its
elements under standard conditions (i.e. 298K,
1 atm)
Mg(s) + ½ O2(g) → MgO(s) ΔHºf = -692 kJmole-1
C(s) + ½ O2(g) → CO2(g) ΔHºf = -393.7 kJmole-1
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Standard Enthalpy of Atomization (ΔHºatm)
22

It is the amount of heat absorbed when

one mole of element is converted to
gaseous atom under standard conditions.
(298 K, 1 atm)
Na(S)  Na(g) ΔHºatm = +108kJmole-1

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 Standard Enthalpy of Neutralization:- (ΔHºn)
23
It is amount of heat evolved or absorbed when one mole of H + ion
from an acid reacts. With one mole of OH - ions from a base to
form one mole of H2O under standard conditions.
Consider neutralization of HCl and NaOH
HClaq H+aq + Cl-aq

NaOHaqNa+aq + OH-aq

Na+aq + OH-aq + H+aq + Cl-aq  NaClaq + H2O

H+ + OH-  H2O ΔHn = -57.4kJ/mole 6/25/19

Enthalpy of neutralization is merely the heat formation of one mole of liquid
water form its ionic components.
 Energy of neutralization may be positive
24

Whenever the acids or bases or both are weak

then the amount of energy evolved is less
negative than -57.4 kJmole-1. For very weak
acids heat of neutralization is positive. It means
that energy is required to break molecules of
such acids and bases into ions
eg ΔHn (HCN) = + 45.6 kJmole-1 6/25/19
Standard Enthalpy of Combustion (ΔHºC)
25

• It is enthalpy change, when one mole

of a substace is completely burnt in
excess of oxygen under standard
conditions i.e. 298k and 1 atm.

• C(g) + O2(g)  CO2(g)ΔH0c = -393.7 kJmole-1

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Standard Enthalpy of Solution (ΔHºsol)
26

The amount of heat absorbed or evolved when

one mole of a substance is dissolved in so
much of water that further dilution results in no
detectable heat change.

• NH4Cl(S)  NH4Cl(aq) ΔHº = +15.1 kJmole-1

• Na2CO3(5)  Na2CO3 (aq) ΔHºs = -250 kJ mole-1
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Glass Calorimeter 27

q = m s ΔT
Δ H = q/n

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Bomb Calorimeter 28

q = C ΔT
Δ H = q/n

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 1) First Law of thermochemistry:-
29

The amount of heat required to decompose a

compound into its elements is equal to the
heat evolved when that compound is formed
from its elements

• ½ N2(g) + 3/2 H2(g)  NH3(g) ΔHf = -46.11 kJmole-1

• NH3(g)  1/2 N2(g) + 3/2 H2(g) ΔHd =+46.11 kJmole-1
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2) Second Law of thermochemisry:-
30

The enthalpy change of a system depends

upon its initial and final states only and is
independent of the path followed by the
system
The enthalpy change in a chemical reaction will be the
same whether it completes in one step or several steps.
Consider a hypothetical reaction, in which a substance
‘A’ is converted into D by directly in single step and
indirectly in three steps 6/25/19
Proof of Hess’s Law 27

• Single step
• 2NaOH(aq) + CO2(g)  Na2CO3(aq) ΔH2 = -48.06kJ
• Two Steps
NaOH(aq) + CO2(g)  NaHCO3 (aq) ΔH2 = -48.06kJ
NaHCO3 (aq) + NaOHaq  Na2CO3(aq) + H2O(l) ΔH3 =-41.02kJ
• According to Hess’s law
ΔH1 = ΔH2 + ΔH3
• Putting the value of ΔH1, ΔH2 and ΔH3 in above (aq)
-89.08 = -48.06 – 41.02
-89.08 = -89.08
LHS = RHS 6/25/19

Hence the law is verified

Born Haber Cycle:-
32

• It states that energy change in a cyclic process is

always zero.
• ΣΔH(cycle) = 0
• It enable us to calculate the lattice energy of binary
ionic compounds such as M+X-

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Lattice energy 33

The lattice energy of an ionic crystal is the

enthalpy of formation of one mole of the ionic
compound from gaseous ions under standard
conditions.

• Na(g)+ + Cl-(g)  Na+Cl-(S) ΔHolattice = -787 KJmole-1

• Lattice energy cannot be determined directly but

obtained indirectly by means of an energy cycle.
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 Born Haber cycle (energy
34
triangle)

Comparing this cycle with the energy triangle for

sodium chloride it is clear that
ΔHx = ΔHat(Na) + ΔH2(Na) + ΔHD/2(Cl2) + ΔH2(Cl2)
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Born-Haber Cycle (energy Profile Diagram) 35

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 Born-Haber Cycle 36
The first two steps are for the enthalpy changes due to
i) enthalpy of atomization
Na(S)  Na(g) ΔHatm = +108kJmole-1
ii) enthalpy of ionization
Na(g)  Na+(g) = le- ΔHion = + 496 kJmole-1
The 2nd two steps are for the enthalpy changes due to
ii) enthalpy of dissociation
½ Cl2(g)  Cl(g) ΔHdis = + 122kJmole-
ii) enthalpy of electron affinity

Cl(g) + le-  Cl-(g) ΔHe = -349kJmole-1 6/25/19

Born-Haber CYCLE 37

ΔHof = ΔHo latt + ΔHox

ΔHo latt = ΔHof - ΔHox

ΔHo latt = ΔHof - (ΔHat(Na) + ΔH2(Na) + ΔHD/2(Cl2) + ΔH2(Cl2))

ΔHo latt = -411 - (108+ 496 + 121 - 349)

ΔHo latt = -411 - 376

ΔH olatt = -787kJmole 6/25/19