System and Surroundings: -

System:-

A specified part of the universe which is under observation is called the system. A system is
homogenous if physical properties and chemical composition are identical throughout the system. A
system is heterogeneous if it consists of parts (or phases) each of which has different physical and
chemical properties. A homogenous system consists of one phase while a heterogeneous system
consists of two or more phases.

Surrounding:-

The remaining portion of the universe which is not a part of the system is called the
surroundings. In other words, surroundings include everything other than the system. The system and
the surroundings together constitute the universe.

System + Surroundings = Universe

1. Open System:-

A system which can exchange matter as well as energy with the surroundings is called an open
system. (e.g) hot coffee in open flask,

Zn+HCl in a open beaker

2. Closed System:-

A system which can exchange energy but not matter with its surrounding is called a closed
matter. (e.g) hot coffee in a stainless steel Cup
∆
HI→H2+I2 in a sealed glass bulb

3. Isolated system:-

A system which can neither exchange matter nor energy with the surroundings is called an
isolated system. (e.g) there is no perfectly isolated system.

Reactants in closed thermos flask

All physical and chemical processes taking place in open in our daily life are open system
because these are continuously exchanging matter and energy with the surroundings.

State Variable:-

The measurable properties required to describe the state of the system are called state
variables. (e.g) temp, pressure, volume, composition.
State Function:-

A state function is a property of the system whose value depends only upon the state of the
system and is independent of the path or manner by which the state is reached. The change in the value
of these properties depends only on initial & final states of the system and not on the path by which it
reaches the final state. Some common state functions are pressure(P), temperature(T), internal
energy(U), enthalpy(H), entropy(S), etc.,

Thermodynamic Equilibrium:-

A system is said to be in thermodynamic equilibrium if its macroscopic properties (like

temperature, pressure, etc.,) do not change with time.

Internal energy as a state function:-

Every substance possess a definite quantity of energy which depends upon factors such as
chemical nature of the substance, temperature and pressure. This is known as intrinsic energy or
internal energy and is represented by the symbol U. The sum of all forms of energy (chemical , electrical,
mechanical etc.,) stored within a substance (or a system) is called its internal energy. The change in the
internal energy of a reaction may be considered as the difference between the internal energies of the
two states.

Let UA and UB are the internal energies in the states A and B respectively. Then the difference
between the internal energies in the two states will be

∆𝑈 = 𝑈𝐵 − 𝑈𝐴

The difference between the internal energies of the product and that of the reactants is

∆𝑈 = 𝑈𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠 − 𝑈𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠 = 𝑈𝑝 − 𝑈𝑟

∆𝑈 depends on

1. Heat passes into or out of the system

2. Work is done on or by the system
3. Matter enters or leaves the system

Modes of transfer of energy:-

1. Heat:- (q)
Energy is (transferred) exchange between the system and the surroundings as heat if
they are at different temperatures. There is a flow of heat from system to surroundings
if the system has higher temperature and there is a flow of heat from surroundings to
the system if the former is at higher temperature. This exchange of energy which is a
result of temperature difference is called q.
 ∆𝑈 = 𝑞 = 𝑇𝐵 − 𝑇𝐴
TA- Temperature of water in container
TB- huge heat in reservoir
q is positive when heat is transferred from the surroundings to the system.
q is negative when heat is transferred from the system to the surroundings.

2. Work(w):-

Work is said to be performed if the point of application of force is displaced in the direction of
force. It is equal to the force multiplied by displacement.

w =f xdl

There are two types of work

1. Electrical work
2. Mechanical work

The system which would not allow exchange of heat between the system and the surroundings through
its boundary is called adiabatic system. The process in which there is no transfer of heat between the
system and surroundings is called adiabatic process. The boundary wall which does not allow the heat
exchanger between system and surroundings is adiabatic wall. Let us bring the change in internal energy
by doing some work on the system. Let the intial state of the system be state A and its temperature be
TA. Let the internal energy of the system in state A be U A. We can change the state of the system in two
different ways.

1. One way:-
Suppose we do some mechanical work (say 1KJ) by rotating a set of small paddles and
there by churning the water, this will convert all the mechanical energy of the rotating paddle
into heat by friction between paddles and water. This heat energy will result into rise of
temperarture. Let the next state be called state B and its temperature be TB (TB>TA). Let the
internal energy of the system in state B be UB and change in the internal energy.
∆𝑈 = 𝑈𝐵 − 𝑈𝐴
2. Second way:-
Let us assume we do an equal amount of electrical work (1KJ). We heat the water with
the help of immersion rod. It will be observed that change in temperature is same in
earlier case TB-TA.
Joule found that a given amount of work done on the system, no matter how it was
done (irrespective of path) always produced the same change of state as measured by
the change in the temperature of the system.
We observe that the value of internal energy is characteristic of the state of a system
and the adiabatic processes Wad required to bring about a change is equal to the
difference between the value of U in one state and that in another state.
∆𝑈 = 𝑈𝑓𝑖𝑛𝑎𝑙 − 𝑈𝑖𝑛𝑡𝑖𝑎𝑙 = 𝑊𝑎𝑑
 Thus internal energy U of the system is a state function. The positive sign express that
Wad is positive, when work is done on the system. Similarly if work is done by the
system, Wad is negative.

3. General Case:-
Let us consider the general case in which a change of state is brought about both by
doing work and by transfer of heat. We write change in internal energy as
∆𝑈 = 𝑞 + 𝑤
However ∆𝑈 depend only on initial & final states. It will be independent of the way the
change is carried out. If there is no transfer of energy as heat or as work (isolated
system) if W=0 & q=0, then ∆𝑈=0.

First law of Thermodynamics:-

The energy of an isolated system is constant in first law of thermodynamics.

∆𝑈 = 𝑞 + 𝑤

It is commonly known as law of conservation of energy that is energy can neither be created nor
be destroyed.

∆𝑈 is the change in enthalpy

q is the heat added to the system

w is the work done on the system

Pressure-Volume work:-

Let us consider a cylinder which contains one mole of an ideal gas fitted with a frictionless
piston. Total volume of the gas in the initial step is Vi and pressure of the gas inside is P, if external
pressure is Pex which is greater than P, piston is moved inwards, till the pressure inside becomes equal to
Pex, let this change be achieved in single step & volume at final stage be Vf. During this compression,
suppose piston moves a distance ‘l’ and cross-sectional area of the piston is A then,

Volume change= lxA = ∆V= Vf- Vi

𝑓𝑜𝑟𝑐𝑒
Pressure= 𝑎𝑟𝑒𝑎

Force on Piston= Pex.A

Work = force x distance

= Pex.A x l
 =Pex(-∆V)

=-Pex(Vf-Vi)

The negative sign of this expression is required to obtain conventional sign for w, which will be positive.
It indicates that in case of compression Vf is smaller, thus Vf-Vi is negative hence work will be positive.

If the pressure is not constant at every stage of compression, but changes in number of finite steps,
work done on the gas will be summed overall the steps and will be equal to -∑ 𝑃∆𝑉. If the pressure is
not constant but changes during the process such that it is always infinitesimally greater than the
pressure of the gas, then at each stage of compression, the volume decreases by an infinitesimally
amount dV. In such a case we can calculate the work done on the gas by relation.
𝑓
𝑊 = − ∫𝑉 𝑃𝑒𝑥 . 𝑑𝑉 →1
𝑖
Here Pex at each stage is Pin+ dp in case of compression, but in case of expansion process

𝑃𝑒𝑥 = (𝑃𝑖𝑛 − 𝑑𝑃 ), in general case we can write

𝑃𝑒𝑥 = (𝑃𝑖𝑛 ± 𝑑𝑃 ) → 2 For reversible process

Substituting 2 in 1
𝑉 𝑉
𝑊𝑟𝑒𝑣 = − ∫𝑉 𝑓 𝑃𝑒𝑥 . 𝑑𝑉 = − ∫𝑉 𝑓(𝑃𝑖𝑛 ± 𝑑𝑃). 𝑑𝑉
𝑖 𝑖

Since dP x dV is very small

𝑉
𝑊𝑟𝑒𝑣 = − ∫𝑉 𝑓 𝑃𝑖𝑛 . 𝑑𝑉
𝑖

𝑛𝑅𝑇
By writing Pin as p and applying ideal gas eqn. p= 𝑉
, then

𝑉 𝑛𝑅𝑇 𝑉 𝑑𝑉
𝑊𝑟𝑒𝑣 = − ∫𝑉 𝑓 𝑉
. 𝑑𝑉 = − ∫𝑉 𝑓 𝑛𝑅𝑇 . 𝑉
𝑖 𝑖

𝑉𝑓 𝑉𝑓
= 𝑛𝑅𝑇(𝑙𝑛 ) = -2.303nRT log
𝑉𝑖 𝑉𝑖

Free Expansion:-

Expansion of a gas in vacuum Pex=0 is called free expansion. No work is done during free
expansion of an ideal gas whether the process is reversible or irreversible.

𝑊 = −𝑃𝑒𝑥 . ∆𝑉 → 1

We know

∆𝑈 = 𝑞 + 𝑤 →2

Substituting 2 in 1

∆𝑈 = 𝑞 − 𝑃𝑒𝑥 . ∆𝑉

If a process is carried out at constant volume ∆𝑉 = 0, then (iso choric process)

∆𝑈 = 𝑞𝑣

Isothermal & free expansion of an ideal gas:-

Isothermal so T=constant

Expansion of ideal gas in vaccum w=0

Pex=0

∆𝑈 = 𝑞 + 𝑤
 a) For isothermal irreversible change
𝑞 = −𝑊 = 𝑃𝑒𝑥 (𝑉𝑓 − 𝑉𝑖 )
b) For isothermal reversible change
𝑉𝑓 𝑉𝑓
𝑞 = −𝑊 = 𝑛𝑅𝑇𝑙𝑛 = +2.303𝑛𝑅𝑇𝑙𝑜𝑔
𝑉𝑖 𝑉𝑖
c) For adiabatic change
q=0 ∆𝑈 = 𝑊𝑎𝑑

Enthalpy:-

The heat absorbed at constant volume is equal to change in the internal energy that is ∆𝑈 = 𝑞𝑣
most of the reactions are carried out in constant pressure (atm. Pressure) but not at constant volume,

∆𝑈 = 𝑞𝑝 − 𝑝. ∆𝑉 at constant pressure, where qp is the heat absorbed

𝑝. ∆𝑉 is work done on expansion

Let us represent intial & final state by 1 & 2 subscripts.

∆𝑈 = 𝑈2 − 𝑈1

=qp-p(V2-V1)

U2-U1 =qp-p(V2-V1)

qp =U2-U1 +p(V2-V1)

=U2-U1 +pV2 – pV1

=U2 + pV2- U1- pV1

=(U2 + pV2) – (U1 + pV1)

=H2-H1

We can define another thermodynamic function enthalpy, H(greek word enthalpien to warm) or heat
content as

H=U+pV

qp=H2-H1=∆H (qp is heat absorbed at constant pressure).

qp is independent of path. Thus H is a state function(H is function of U,p and V which are all state
functions). Thus ∆H is independent of path. Thus enthalpy of a system may be defined as “The sum of
the internal energy and the product of its pressure and volume.”

∆H= Heat evolved or absorbed in a reaction at constant temperature and constant pressure.
 The enthalpy change of a reaction is equal to the heat absorbed or evolved during a reaction at
constant temperature and pressure. ∆H is negative for exothermic reactions which evolve heat during
the reaction and ∆H is positive for endothermic reaction.(reactions which absorb heat from the
surroundings).

∆H= +ve exothermic reactions

∆H= -ve endothermic reactions

At constant volume ∆V=0, ∆U=qv

∆𝐻 = ∆𝑈 = 𝑞𝑣

Let us assume

VA Volume of reactants gases

VB Volume of product gases

nA number of moles of reactant

nB number of moles of products

all at constant pressure.

pVA=nA.RT; pVB=nBRT

pVB-pVA=nBRT-nART

=RT(nB-nA)

p.∆V =RT.∆ng

where ∆ng is the difference between number of moles of gaseous products & gaseous reactants.

∆𝐻 = ∆𝑈 + 𝑅𝑇. ∆𝑛𝑔

Extensive & intensive properties: -

An extensive property is a property whose value depends on the quantity or size of matter
present in the system. For example mass, volume, internal energy, enthalpy, heat capacity,etc.,

An intensive property is a property which does not depend on the quantity or size of matter
present in the system.

Example: - Temperature, pressure, density etc.,

Heat Capacity:-

The increase in temperature is proportional to the heat transferred.

q = coefficient x ∆𝑇

=C. ∆𝑇

Where C is the heat capacity and is directly proportional to the amount of substance. Heat capacity is
defined as “the amount of heat required to raise the temperature of the system by one degree”.

Specific head Capacity:-

Specific heat capacity (Molar heat capacity) is the heat capacity for one mole of the substance
and is the quantity of heat needed to raise the temperature of one mole by one degree Celsius. Specific
heat capacity is defined as the heat required to raise the temperature of one unit mass of substance by
one degree Celsius”.

q=c x m. ∆𝑇 =C. ∆𝑇

c- specific heat

m- mass

C- Heat capacity

Relationship between Cp & Cv:-

C is heat capacity

Cp is heat capacity at constant pressure

Cv is heat capacity at constant volume

At constant volume.

𝑞𝑣 = 𝐶𝑣 . ∆𝑇 = ∆𝑈 →1

At constant pressure

𝑞𝑝 = 𝐶𝑝 . ∆𝑇 = ∆𝐻 →2

The difference between Cp and Cv can be derived for an ideal gas as where n=1

∆𝐻 = ∆𝑈 + 𝑃. ∆𝑉

= ∆𝑈 + ∆. 𝑅𝑇

= ∆𝑈 + 𝑅. ∆𝑇 →3
Substituting 1 & 2 in 3

Cp. ∆𝑇= Cv. ∆𝑇 + R. ∆𝑇

C P= C v + R

Cp-Cv=R

Similarly for n moles of an ideal gas

Cp-Cv=nR

Measurement of ∆𝑼 & ∆𝑯 :-

Calorimetry:-

Measurements are made under two different conditions

a) At constant volume qv
b) At constant pressure qp

a) ∆𝑈 meaurements:-
Heat absorbed at constant volume is measured in a bomb calorimeter. A steel vessel
(the bomb) is immersed in a water bath. The whole device is called calorimeter. The
steel vessel is immersed in water bath that no heat is lost to the surroundings. A
combustible substance is burnt in pure dioxygen supplied in steel bomb, since the bomb
calorimeter is scaled, its volume does not change, the energy changes associated with
reactions are measured at constant volume. No work is done as the reaction is carried
out at constant volume in the bomb calorimeter. Even for reactions involving gases,
there is no work done as ∆𝑉=0. Temperature change of the calorimeter produced by the
completed reactions is converted as qv by using the heat capacity (known) of
calorimeter.
 b) ∆𝐻 meaurements:-
Measurement of heat change at constant pressure (generally under atmospheric
pressure) can be done in calorimeter
∆𝐻 = 𝑞𝑝 = ∆𝛾 𝐻
Heat absorbed at constant pressure is also called as heat of reaction. In an exothermic
reaction, heat is evolved and system loses heat to the surroundings. Therefore qP will be
negative and ∆𝛾 𝐻 will also be negative. Similarly in endothermic reactions, heat is
absorbed qP is positive & ∆𝛾 𝐻 will also be positive.

Enthalpy change-reaction Enthalpy:-

Reactants → Products

The enthalpy change accompanying a reaction is called the reaction enthalpy ∆𝑟 𝐻.

∆𝑟 𝐻= Sum of enthalpies of products – Sum of enthalpies of reactant

= ∑𝑖 𝑎𝑖 𝐻𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠 − ∑𝑖 𝑏𝑖 𝐻𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠

Where ai and bi are stoichiometric coefficients of products and reactants

CH4 + 2O2 → CO2 +2H2O

∆𝛾 𝐻 =[Hm CO2(g) + 2HmH2O(l)]-[HmCH4 + 2HmO2(g)]

Where Hm is molar enthalpy

Standard enthalpy:- ∆𝑯−

The standard state of a substance at a specified temperature is its pure form at 1 bar. The
standard enthalpy of reaction is the enthalpy change for a reaction when all the participating substance
are in their standard states.
Enthalpy of fusion: -∆𝒇𝒖𝒔 𝑯−

The (enthalpy) amount of heat required for melting one mole of solid substance in standard state is
called standard enthalpy of fusion (Molar Enthalpy of Fusion)

Standard enthalpy of sublimation: -∆𝒔𝒖𝒃 𝑯−

Standard enthalpy of sublimation∆𝑠𝑢𝑏 𝐻 − is the change in enthalpy when one mole of a solid
substance sublimes at a constant temperature and under standard pressure (1 bar).

c) Standard Enthalpy of formation:- ∆𝒇 𝑯−

The standard enthalpy change for the formation of one mole of a compound from its elements
in their most stable states of aggregation is called standard molar enthalpy of formation(25℃, 1 bar)

𝐶(𝑔𝑟𝑎𝑝ℎ𝑖𝑡𝑒 𝑆) + 2𝐻2(𝑔) → 𝐶𝐻4(𝑔) ∆𝑓 𝐻 − = −74.81𝐾𝐽/𝑚𝑜𝑙

1
2𝐶(𝑔𝑟𝑎𝑝ℎ𝑖𝑡𝑒 𝑆) + 3𝐻2(𝑔) + 2 𝑂2(𝑔) → 𝐶2 𝐻5 𝑂𝐻(𝑙) ∆𝑓 𝐻 − = −277.7𝐾𝐽/𝑚𝑜𝑙

In above equations 1 mole of product is formed from its constituent elements, if 2 moles of
product are formed then,

𝐻2(𝑔) + 𝐵𝑟2(𝑙) → 2𝐻𝐵𝑟 ∆𝛾 𝐻 = −72.8 𝐾𝐽/𝑚𝑜𝑙

2∆𝑓 𝐻− = ∆𝑟 𝐻

∆𝑟 𝐻 72.8
∆𝑓 𝐻 − = 2
=− 2
= −36.4𝐾𝐽/𝑚𝑜𝑙

In contrast, the enthalpy change for exothermic reaction

CaO(s) + CO2(g) → CaCO3(s) ∆𝑟 𝐻 − = −178.3𝐾𝑗/𝑚𝑜𝑙 is the enthalpy of formation of calcium

carbonate as it is not formed from its constituent elements. The enthalpy of decomposition of a
compound can be found from its enthalpy of formation of its products and reactants.

CaCO3(s) → CaO(s) + CO2(g) ∆𝑟 𝐻 − =?

∆𝑟 𝐻 − = ∑ 𝑎𝑖 ∆𝑓 𝐻− 𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠 − ∑ 𝑏𝑖 ∆𝑓 𝐻− 𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠 (a&b are co-efficient hence it is 1)

= 1(−635.1𝐾𝐽/𝑚𝑜𝑙) + 1(−393.5𝐾𝐽/𝑚𝑜𝑙) − 1(−1206.9𝐾𝐽/𝑚𝑜𝑙)

= −635.1 − 393.5 + 1206.9

= −1028.6 + 1206.9

= +178.3𝐾𝐽/𝑚𝑜𝑙

The above calculation reveals the decomposition of calculation is an endothermic process.

 d) Thermodynamic reactions:-
Conventional assumptions in thermochemical equations are
 The co-efficient in a balanced thermochemical equation refer to the number of
moles of reactant & products involved in the reaction.
 The numerical value of ∆𝑟 𝐻− refers to the number of moles of substance
specified by an equation. Standard enthalpy change ∆𝑟 𝐻 − will have units as
KJ/mol.
Fe2O3(s)+3H2(g)→2Fe(s) + 3H2O(l)
∆𝑓 𝐻 − (H2O(l)) = -285.83KJ/mol
∆𝑓 𝐻 − (Fe2O3(l))= -824.2KJ/mol
∆𝑓 𝐻 − (Fe(s))=0
∆𝑓 𝐻 − (H2(g))=0
∆𝑟 𝐻 − =3(-285.83)-(-824.2)
=-857.5 + 824.2
−
∆𝑟 𝐻 = -33.3KJ/mol
If we balance the eqn. in the following way
1 3 3
2
𝐹𝑒2 𝑂3(𝑠) + 2 𝐻2(𝑔)→ 𝐹𝑒 + 2 𝐻2 𝑂(𝑙)
3 1
∆𝑟 𝐻 − = 2 (−285.83) − 2 (−824.2) = −428.7 + 412.1
∆𝑟 𝐻 − = −16.6𝐾𝐽/𝑚𝑜𝑙
Thus we understood enthalpy is an extensive property which depends on matter
present.
 When a chemical eqn is reversed, the value of ∆𝑟 𝐻 − is reversed in sign
N2(g)+3H2(g)→2NH3(g) ∆𝑟 𝐻 − =-91.8KJ/mol
2NH3(g)→N2(g)+3H2(g) ∆𝑟 𝐻 − = +91.8KJ/mol
e) Hess Law of constant heat summation:-
If a reaction takes place in several steps then its standard reaction enthalpy is
the sum of standard enthalpies of the intermediate reactions into which the overall
reactions may be divided at the same temperature.
1
C(graphite,s)+2O2(g)→CO(g) ∆𝑟 𝐻 − =?
C(graphite,s)+O2→CO2 ∆𝑟 𝐻 − =-393.5KJ/mol
1
CO(g) + 2O2→CO2 ∆𝑟 𝐻 − =-283.0KJ/mol
C(graphite,s)+ O2→ CO2(g) ∆𝑟 𝐻 − =-393.5KJ/mol
1
CO2(g) → CO(g) + 2O2(g) ∆𝑟 𝐻 − =+283.0KJ/mol

1
C(graphite,s) + 2O2(g) → CO(g) ∆𝑟 𝐻 − =-110.5KJ/mol

In general if enthalpy of an overall reaction A→B as ∆𝑟 𝐻 and its different steps (as
shown below) summation of enthalpies.
∆𝑟 𝐻 = ∆𝑟 𝐻1 + ∆𝑟 𝐻2 + ∆𝑟 𝐻3 ∆𝑟 𝐻 = ∆1 𝐻 + ∆2 𝐻

∆𝑟 𝐻 = ∆𝐻1 + ∆𝐻2

Enthalpies of different types of reactions:-

a) Standard enthalpy of combustion ∆𝒄 𝑯−

The enthalpy change (or heat change) when one mole of a substance is completely
burnt in excess of oxygen or air is called enthalpy of combustion (reactants & products
in their standard state). It may be noted that the enthalpy of combustion ∆c H − is
always negative because combustion reaction are always exothermic heat is evolved
during combustion.
C(s) + O2(g) → CO2(g) ∆𝑐 𝐻=-393.5KJ/mol
CH4(g) + 2O2(g) → CO2(g) + 2H2O(l) ∆𝑐 𝐻 − =-890.3KJ
13
C4H10(g) + 2
O2(g) → 4CO2(g) + 5H2O(l) ∆𝑐 𝐻 − =-2658.0KJ/mol
b) Enthalpy of atomization:-
The enthalpy change on breaking one mole of bonds completely to obtain atoms in the
gas phase.
H2(g) → 2H(g) ∆𝑎 𝐻 − =435KJ/mol
The enthalpy of atomization can also be known as enthalpy of bond dissociation.
CH4(g) → C(g) + 4H(g) ∆𝑎 𝐻 − =1665KJ/mol
Na(s) → Na(g) ∆𝑎 𝐻 − =108.4KJ/mol

c) Bond Enthalpy-polyatomic Molecules:-

In methane all four C-H bonds are identical in bond length and energy. However the
energies required to break the individual C-H bonds in each successive step differ.
CH4(g) → CH3(g) + H(g) ∆𝑏𝑜𝑛𝑑 𝐻 − =+427KJ/mol
CH3(g) → CH2(g) + H(g) ∆𝑏𝑜𝑛𝑑 𝐻 − =+439KJ/mol
CH2(g) → CH(g) + H(g) ∆𝑏𝑜𝑛𝑑 𝐻 − =+452KJ/mol
CH(g) →C(g) + H(g) ∆𝑏𝑜𝑛𝑑 𝐻 − =+347KJ/mol

CH4(g) → C(g) + 4H(g) ∆𝑏𝑜𝑛𝑑 𝐻 − =1665KJ/mol

 We use mean bond enthalpy of C-H bond
1 1
∆𝐶−𝐻 𝐻 − = 4 (∆𝑎 𝐻− ) = 4 (1665) = 416KJ/mol

The standard enthalpy of reaction,∆𝑟 𝐻 − is related to bond enthalpies of the reactants and products in
gas phase reactions as

∆𝑟 𝐻 − = ∑ 𝑏𝑜𝑛𝑑 𝑒𝑛𝑡ℎ𝑎𝑙𝑝𝑖𝑒𝑠 𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠 − ∑ 𝑏𝑜𝑛𝑑 𝑒𝑛𝑡ℎ𝑎𝑙𝑝𝑖𝑒𝑠 𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠

The net enthalpy change of a reaction is the amount of energy required to break all the bonds in the
product reactant molecules minus the amount of energy required to break all the bonds in the product
molecules.

d) Enthalpy of solution:- ∆𝒔𝒐𝒍 𝑯−

The enthalpy of solution of a substance is the enthalpy change when one mole of it
dissolves in a specified amount of solvent. The enthalpy of hydration is defined as the
enthalpy change (heat evolved or absorbed) when one mole of anhydrous salt combines
with the required number of moles of water to form hydrated salt. When an ionic
compound dissolves in a solvent, the ions leave their ordered position on the crystal
lattice. These are now more free in solution. Solvation of these ions (hydration in case of
water) also occurs at the same time

∆𝑠𝑜𝑙 𝐻 − = ∆𝑙𝑎𝑡𝑡𝑖𝑐𝑒 𝐻− + ∆ℎ𝑦𝑑 𝐻−

For most of the ionic compound ∆𝑠𝑜𝑙 𝐻 − is endothermic, thus their solubility increase
with temperature. Many fluuroids are less soluble than their corresponding chlorides as
fluorides lattice enthalpies are very high & dissociations of these compounds do not
take place at all. The same explanation can be given for the solubility of Na 2SO4 in water
but BaSO4(bivalent barium lattice enthalpy is more) is insoluble in water.
Lattice Enthalpy:-

The lattice enthalpy of an ionic compound is the enthalpy change which occurs when one mole
of an ionic compound dissociates into its ions in gaseous state.

NaCl(s)→ Na(g)+ + Cl(g)- ∆𝐻° lattice

The overall process is thought to take place in the following steps

a) Conversion of metallic sodium into gaseous sodium atom – enthalpy of sublimation

Na(s)→Na(g) ∆𝑠𝑢𝑏 𝐻° = 108.4𝐾𝐽/𝑚𝑜𝑙
b) Dissociation of chlorine molecules into chlorine atoms-enthalpy of atomization
Cl2(g) → 2Cl(g) ∆𝐻 = 242𝐾𝐽/𝑚𝑜𝑙
1
2
Cl2(g) →Cl(g) ∆𝑎 𝐻° = 121𝐾𝐽/𝑚𝑜𝑙
c) Conversion of gaseous sodium atoms into sodium ions-ionization enthalpy
Na(g)→Na(g)+ + e- ∆𝑖 𝐻° = 495.6𝐾𝐽/𝑚𝑜𝑙
d) Conversion of gaseous chlorine atoms into chloride atoms ions-electron gain enthalpy
Cl(g) + e- → Cl-(g) ∆𝑒𝑔 𝐻° = −348.6𝐾𝐽/𝑚𝑜𝑙
e) Combination of oppositely charged ions to form a solid crystal-lattice enthalpy
Na(g)+ +Cl-(g) → NaCl(g) ∆𝑙𝑎𝑡𝑡𝑖𝑐𝑒 𝐻°

Born Haber Cycle:-

1
∆𝑓 𝐻° = ∆𝑠𝑢𝑏 𝐻° + ∆𝑖 𝐻° + ∆𝑎 𝐻° + ∆𝑒𝑔 𝐻° + ∆𝑙𝑎𝑡𝑡𝑖𝑐𝑒 𝐻°
2
-411.2KJ = 108.4+495.6+121-348.6+∆𝑙𝑎𝑡𝑡𝑖𝑐𝑒 𝐻°
=725-348.6+∆𝑙𝑎𝑡𝑡𝑖𝑐𝑒 𝐻°
 =376.4+∆𝑙𝑎𝑡𝑡𝑖𝑐𝑒 𝐻°
-787.6 =∆𝑙𝑎𝑡𝑡𝑖𝑐𝑒 𝐻° (lattice Enthalpy)
NaCl →Na(g)+ + Cl(g) - ∆𝑙𝑎𝑡𝑡𝑖𝑐𝑒 𝐻° = 787.6𝐾𝐽/𝑚𝑜𝑙
We know∆𝑠𝑜𝑙 𝐻=∆𝑙𝑎𝑡𝑡𝑖𝑐𝑒 𝐻° + ∆ℎ𝑦𝑑 𝐻° lattice enthalpy is known & enthalpy of hydration is -
784.1KJ/mol
∆𝑠𝑜𝑙 𝐻 − = 787.6 − 784.1
= +3.5KJ/mol.
This dissolution of sodium chloride is accompanied by a very small heat change.

Spontaneity of process:-

A process which can take place by itself under the given set of conditions once it has been
initiated if necessary is said to be a spontaneous process. A spontaneous process is an irreversible
process and may only be reversed by some external agency.

a) Enthalpy changes-decrease and increase-criteria for spontaineity:-

1 3
2
𝑁2(𝑔) + 2 𝐻2(𝑔) → 𝑁𝐻3(𝑔) ∆𝑟 𝐻 − = −46.1𝐾𝐽/𝑚𝑜𝑙
1 1
2
𝐻2(𝑔) + 2 𝐶𝑙2(𝑔) → 𝐻𝐶𝑙(𝑔) ∆𝑟 𝐻 − = −92.32𝐾𝐽/𝑚𝑜𝑙
1
𝐻2(𝑔) + 2 𝑂2(𝑔) → 𝐻2 𝑂(𝑔) ∆𝑟 𝐻 − = −285.8𝐾𝐽/𝑚𝑜𝑙

In the above examples the decrease in enthalpy from reactants to products(exothermic) may acts as a
driving force for a chemical reaction. In the following examples the increase in enthalpy from reactants
to products(endothermic) may act as a contributory factor for spontaneity. Then its found the
spontaneous process are driven by entropy.

Randomness or Disorder:-

Spontaneity of a process is determined by

a) Tendency of a system to acquire a state of minimum energy

b) Tendency of a system to acquire a state of maximum randomness

The extent of disorder or randomness in a system may be expressed by a thermodynamic property

known as entropy. Entropy may be defined as”the property of a system which measures the degree of
disorder or randomness in the system.” The change in entropy during the process when a system
undergoes a change from one state to another is represented by ∆𝑆

∆𝑆 = 𝑆𝑓𝑖𝑛𝑎𝑙 𝑠𝑡𝑎𝑡𝑒 − 𝑆𝑖𝑛𝑖𝑡𝑖𝑎𝑙 𝑠𝑡𝑎𝑡𝑒

∆𝑆 = 𝑆𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠 − 𝑆𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠

∆𝑺 = +𝒗𝒆 :-

For chemical reactions, entropy change is attributed to change in rearrangement of atoms or

ions in the reactants, to that of products. If the structure of the products is very much disordered than
that of the reactants, there will be increase in entropy ∆𝑆 is positive. Entropy may also be related to the
heat involved in a process, whenever heat is added to the system, it increases molecular motion
resulting increased randomness in the system. A system at higher temperature has greater randomness
in it than at lower temperature. Temperature is also a measure of average chaotic motion or
𝑞𝑟𝑒𝑣
randomness of particles in the system. For a reversible process ∆𝑆 = 𝑇
where 𝑞𝑟𝑒𝑣 represents the
heat absorbed.

Entropy as a state function:-

𝑞𝑟𝑒𝑣
Change in entropy of the system ∆𝑆𝑠𝑦𝑠 = 𝑇

∆𝑆𝑡𝑜𝑡𝑎𝑙 = ∆𝑆𝑠𝑦𝑠𝑡𝑒𝑚 + ∆𝑆𝑠𝑢𝑟𝑟 > 0

When a system is in equilibrium the entropy is maximum, and the change in entropy∆𝑆 = 0. The total
entropy change ∆𝑆 total for system and surroundings a spontaneous process is given by.
𝑞𝑠𝑦𝑠.𝑟𝑒𝑣
∆𝑆𝑠𝑦𝑠 = 𝑇

We find that both for reversible and irreversible expansion for an ideal gas, under isothermal conditions
∆𝑈 = 0 but

∆𝑆𝑡𝑜𝑡𝑎𝑙 = ∆𝑆𝑠𝑦𝑠𝑡𝑒𝑚 + ∆𝑆𝑠𝑢𝑟𝑟𝑜𝑢𝑛𝑑𝑖𝑛𝑔 not equal to zero for irreversible process

Gibbs Energy:-

Gibbs energy of a system is defined as,”the maximum amount of energy available to a system
during a process that can be converted into useful work”. It is denoted by symbol G and is given by
G=H-TS
Where H is enthalpy
S is entropy
T is temperature
G is an extensive property & a state function
∆𝐺𝑠𝑦𝑠𝑡𝑒𝑚 can be written as
∆𝐺𝑠𝑦𝑠 = ∆𝐻𝑠𝑦𝑠 − 𝑇. ∆𝑆𝑠𝑦𝑠 − 𝑆𝑠𝑦𝑠 ∆𝑇
∆𝐺𝑠𝑦𝑠 = ∆𝐻𝑠𝑦𝑠 − 𝑇. ∆𝑆 ( the last term is 0 as ∆𝑇 = 0)
 ∆𝑆𝑡𝑜𝑡𝑎𝑙 = ∆𝑆𝑠𝑦𝑠 + ∆𝑆𝑠𝑢𝑟𝑟
Increase in enthalpy of the surroundings is equal to decrease in the enthalpy of the system.
∆𝐻𝑠𝑢𝑟𝑟 ∆𝐻𝑠𝑦𝑠
∆𝑆𝑠𝑢𝑟𝑟 = 𝑇
=− 𝑇
∆𝐻𝑠𝑦𝑠
∆𝑆𝑡𝑜𝑡𝑎𝑙 = ∆𝑆𝑠𝑦𝑠 − 𝑇
𝑇. ∆𝑆𝑡𝑜𝑡𝑎𝑙 = 𝑇∆𝑆𝑠𝑦𝑠 − ∆𝐻𝑠𝑦𝑠
For spontaneous process ∆𝑆𝑡𝑜𝑡𝑎𝑙 > 0
𝑇∆𝑆𝑠𝑦𝑠 − ∆𝐻𝑠𝑦𝑠 > 0
−(∆𝐻𝑠𝑦𝑠 − 𝑇∆𝑆𝑠𝑦𝑠 ) > 0

−∆𝐺 > 0

∆𝐺 = ∆𝐻 − 𝑇. ∆𝑆 < 0

∆𝐺is the net energy available to do useful work and is thus a measure of the free energy ∆𝐻𝑠𝑦𝑠
is enthalpy change of a reaction. ∆𝐺 gives a criteria for spontaneity.

i. If ∆𝐺 is negative (< 0),the process is spontaneous

ii. If ∆𝐺 is positive (> 0), the process is non spontaneous.

Gibbs free energy & equilibrium:-

A+B↔C+D

∆𝑟 𝐺 = 0

Gibbs energy for a reaction in which all reactants and products are in standard state ∆𝑟 𝐺 − is related to
the equilibrium constant of the reaction as follows

0 = ∆𝑟 𝐺 − + 𝑅𝑇𝑙𝑛𝑘

∆𝑟 𝐺 − = −𝑅𝑇𝑙𝑛𝑘

= −2.303𝑅𝑇𝑙𝑜𝑔𝑘

∆𝑟 𝐺 − = ∆𝑟 𝐻 − − 𝑇. ∆𝑟 𝑆 − = −𝑅𝑇𝑙𝑛𝑘

∆𝑟 𝐻 − = +𝑣𝑒 for endothermic reaction K< 1

∆𝑟 𝐻 − = −𝑣𝑒 for exothermic reaction K> 1