SPECIAL TUITION FOR PHYSICS CHEMISTRY & BIOLOGY

THERMODYNAMICS
• The study of energy transformations based on initial & final states of a system
undergoing the change.
• Laws of thermodynamics apply only when a system is in equilibrium/ moves from
one equilibrium state to another equilibrium state

THERMODYNAMIC TERMS

a. The System & Surroundings

• System: part of the physical universe which is under study
• System may be defined by physical boundaries, like beaker / test tube/ by a set of
Cartesian coordinates specifying a particular volume in space
• Surroundings: remaining universe other than system which can interact with system.
• For all practical purposes, the surroundings are that portion of the remaining universe
Boundary : real / imaginary wall that separates system from surroundings which to
allow us to control & keep track of all movements of matter & energy in or out of
system
• Universe = System + Surroundings
b. Types of System

i. Open: exchange of energy & matter occur between system & surroundings. E.g.,
reactants taken in an open beaker
ii. Closed: no exchange of matter, but exchange of energy is possible between system &
surroundings. E.g., reactants taken in a closed vessel made of copper/ steel
iii. Isolated: no exchange of energy or matter between the system & surroundings E.g.,
reactants taken in a thermos flask / any other closed insulated vessel
c. The State of System
• Condition of a system at a specific time which is identified by measurable or
macroscopic (bulk) properties called state variables/ state functions
• State functions are those functions which depend only on the state of the
• System & not on how it is reached.
• E.g., pressure (p), volume (V), temperature (T), amount (n), internal energy, enthalpy,
Helmholtz free energy, Gibbs free energy and entropy

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 SPECIAL TUITION FOR PHYSICS CHEMISTRY & BIOLOGY

• They may be further divided into two main types.

i. Extensive property (variable) is one whose value depends upon size of the system.
E.g., volume, weight, heat, etc.
ii. Intensive property (variable) is one whose value is independent of size of the system.
E.g., temperature, pressure, refractive index, viscosity, density, surface tension, etc.
d. Process
• The method of bringing about a change in state
i. Isothermal process: Temperature of system remains constant
E.g., melting of ice
ii. Isochoric process: volume of system remains constant
E.g., pressure cooker
iii. Isobaric process: pressure of system remains constant
E.g., boiling of water
iv. Cyclic process: initial and the final state of a system remain the same
E.g., refrigerator or air conditioner
v. Adiabatic process: there is no exchange of heat between system & surroundings.
• Adiabatic wall - the wall separating the system and the surroundings
vi. Reversible processes: changes are carried out so slowly that system & surroundings
are always in equilibrium
E.g., melting of ice
vii. Irreversible processes: a process that cannot be reversed, which cannot return both
the system and the surroundings to their original conditions.
E.g., electric current flow through a conductor with a resistance, magnetization
viii. Quasi-static process: system is in thermodynamic equilibrium with its surroundings
at all times.
E.g., Mixing of two different gases
e. The Internal Energy, U as a State Function
• Total energy of a closed system which may change, when
i. heat passes into or out of the system,
ii. work is done on or by the system,
iii. Matter enters or leaves the system.
• It is a state function of a system and is an extensive quantity

Prove that Internal energy is Independent of the path (state function)

• Assume that a system is changing with respect to pressure as well as volume. Let ‘A’
be the initial state & ‘B’ is the final state of system with internal energies UA and UB
respectively. Hence Change in internal energy will be given by:
• ΔU = UB – UA
• ∆U is positive if UB > UA
• ∆U will be negative if UB < UA
• Hence change of energy is accompanied as a function of initial & final states of
system only & it is independent of the path.

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 SPECIAL TUITION FOR PHYSICS CHEMISTRY & BIOLOGY

Work

• one of the principal processes by which a thermodynamic system can interact

with its surroundings and exchange energy
• Work done on the system: system's internal energy increased as something outside
the system did work (other than heat flow into the system) on the system
• Work done by the system: system's internal energy decreased as it did work on
something outside the system.
• If state A of a system with temperature TA & internal energy, UA is changed by doing
some mechanical /electrical work, system acquires a new state B with temperature,
TB & internal energy, UB.
• If TB > TA, change in temperature, ∆T = TB–TA & change in internal energy, ∆U
=UB– UA.
• This shows that work done on system, irrespective of path produced same change
of state.
• i.e., ∆U =UB– UA.= wad, adiabatic work required to bring about a change of state
• + ∆U = wad is positive =work is done on the system & ∆U increases.
• -∆U= wad is negative =work is done by the system & ∆U decreases

Heat, q

• Amount of energy transferred

from one system to its
surroundings because of a
temperature difference
• ∆U= q, when no work is done
at constant volume.
• + q = Heat is transferred from
surrounding to system
• -q = Heat is transferred from system to surrounding

First law of thermodynamics: The energy of an isolated system is constant.

• It is commonly stated as the law of conservation of energy i.e., energy can neither be
created nor be destroyed.
• ∆U= q+w

APPLICATIONS

a. Pressure-Volume work
• Volume change, ∆V (Vf – Vi ) = A × l ; Vf = final volume Vi = initial volume
• w = force × distance = Pex ×A × l = pex . (–∆V) = – pex ∆V = – pex (Vf – Vi )
• For isothermal irreversible work, q = -w = pex (Vf – Vi )
vf

• If pressure change is infinitesimally greater than pressure of gas, w = ∫ (p

vi
ex dv )

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 SPECIAL TUITION FOR PHYSICS CHEMISTRY & BIOLOGY

nRT
• From ideal gas equation, P =
V
vf
 dV  V
• − ∫  nRT
At constant temperature (isothermal process), w rev = − nRT ln f
=
vi 
V  Vi
Vf
w = −2.303nRT log
Vi
Vf
q= -w = 2.303nRT log
Vi

Free expansion: S

• Expansion of a gas in vacuum (pex = 0)

• ∆U= q– pex ∆V & at constant volume (∆V = 0), then ∆U =qv

Enthalpy, H [Gk. enthalpien, to warm or heat content]

• Measurement of heat or energy in the thermodynamic system which is equivalent to

the sum of total internal energy and resulting energy due to its pressure and volume.
• H = U + pV
• Enthalpy is a state function as its constituents U, P, and V are state functions

Enthalpy change, ΔH

• - ∆H = exothermic reactions
• +∆H = endothermic reactions
• ΔH = H2 – H1 Where H1 is the initial state enthalpy of the system and H2 is the final
state enthalpy of the system.
• H1 = U1 + P1V1 & H2 = U2 + P2V2
• Using, the values of H1 and H2, value of ΔH will be ΔH = (U2 + P2V2) – (U1+ P1V1)
• ΔH = (U2– U1) + (P2V2 - P1V1)
• ΔH = ΔU + Δ(PV) where ΔU is change in internal energy & Δ(PV) is the change in
product of pressure and volume.
• At a constant pressure P1 = P2 = P; (Isobaric Process)
• ∆H =∆U + P∆V

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 SPECIAL TUITION FOR PHYSICS CHEMISTRY & BIOLOGY

• When Pex = P, then formula for the isobaric process will become, Qp = ΔU +PΔV
• ΔH = Qp (enthalpy of a system is equal to heat absorbed by it at a constant
pressure)
• At constant volume (∆V = 0), isochoric process ∆H = ∆U + 0 = qV

Heat Capacity, C

• Amount of heat energy required to raise the temperature of a body

• The increase of temperature (∆T) is proportional to the heat transferred (q)
q
• q ∝∆T q = C ∆T; C =
∆T
• Water has a large heat capacity i.e., a lot of energy is needed to raise its temperature.

Specific heat capacity (c)

• Quantity of heat required to raise the temperature of one unit mass of a substance by
one degree.
• Heat capacity of a substance is directly proportional to its amount (m).
q
• C ∝ m ; C= c × m ; as C = , q = c ×m ×∆ T
∆T

The Relationship between Cp and CV for an Ideal Gas

• Heat (q) at constant volume is given as qV = CV ∆T= ∆U……..(1)

• Heat (q) at constant pressure is given as qp = Cp∆T= ∆ H……..(2)
• H = U + PV and PV = RT [for one mole of an ideal gas]
• ∴ For ideal gas, ∆H= ∆U + R ∆T……….(3)
• Substituting the values of ∆H in (2) and ∆U in (1) in equation (3) we get,
• Cp ∆T= CV ∆T + R ∆T & Cp - CV = R
• Thus Cp is greater than Cv by the gas constant R

MEASUREMENT OF ∆U AND ∆H: CALORIMETRY

• Calorimetry:
experimental technique
to measure energy
changes associated with
chemical or physical
processes
• It is carried out in a
vessel called
calorimeter immersed in
a known volume of a
liquid with known heat
capacity.

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 SPECIAL TUITION FOR PHYSICS CHEMISTRY & BIOLOGY

a) ∆U Measurements
• For chemical reactions, heat absorbed at constant volume, is measured in a bomb
calorimeter
• The steel vessel (bomb) is immersed in water bath to ensure that no heat is lost to the
surroundings.
• A combustible substance is burnt in pure dioxygen supplied
• Heat evolved during the reaction is transferred to the water around the bomb and its
temperature is monitored.
• Since the bomb calorimeter is sealed, its volume
does not change; ∆V= 0
• Knowing heat Capacity (C) of liquid, q is
calculated using equation, q = C ∆ T
b) ∆H Measurements
• Heat absorbed or evolved, qp at constant
pressure is also called heat of reaction or
enthalpy of reaction, ∆rH.
• For exothermic reaction, qp = negative & ∆rH =
negative.
• For endothermic reaction, qp = positive & ∆rH =
positive

ENTHALPY CHANGE, ∆rH OF A REACTION – REACTION ENTHALPY

• enthalpy change accompanying a reaction

∆r H
•= ∑a H
i
i products − ∑ bi H reac tan ts
i

a) Standard Enthalpy of Reactions, ∆H Θ

• enthalpy change for a reaction when all the participating substances are in their
standard states (its pure form at 1 bar & at specified temperature)

b) Enthalpy Changes during Phase Transformations

i. Enthalpy of fusion or molar enthalpy of fusion, ∆fusH

• Enthalpy change that accompanies melting of one mole of a solid substance in
standard state
• Always positive as reaction is endothermic
ii. Standard enthalpy of vaporization / molar enthalpy of vaporization, ∆ vap H Θ
• Amount of heat required to vaporize one mole of a liquid at constant temperature and
under standard pressure (1bar)
iii. Standard enthalpy of sublimation, ∆ sub H Θ
• change in enthalpy when one mole of a solid substance sublimes at a constant
temperature and under standard pressure (1bar)

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 SPECIAL TUITION FOR PHYSICS CHEMISTRY & BIOLOGY

c) Standard Enthalpy of Formation, ∆ f H Θ

• The standard enthalpy change for the formation of one mole of a compound from its
elements in their most stable states of aggregation (also known as reference states)
• By convention, ∆ f H Θ of an element in reference state, i.e., its most stable state is
taken as zero.

d) Thermochemical Equations
• A balanced chemical equation together with the value of its ∆rH
• E.g., H2(g) + Br2(l) →2HBr(g) ; ∆r H= –178.3k J mol–1
• The coefficients in a balanced thermochemical equation refer to the number of moles
(never molecules) of reactants and products involved in the reaction.
• ∆rH will have units as kJ mol–1.

Hess’s Law of Heat summation

• Hess's law states that the change of enthalpy in a chemical reaction is the same
regardless of whether the reaction takes place in one step or several steps,
provided the initial and final states of the reactants and products are the same.
• Standard reaction enthalpy for a multistep reaction is the sum of the standard
enthalpies of intermediate reactions taken place in the same temperature

ENTHALPIES FOR DIFFERENT TYPES OF REACTIONS

1. Standard Enthalpy of Combustion, ∆ c H Θ

• Enthalpy change per mole (or per unit amount) of a substance, when it undergoes
combustion and all the reactants and products being in their standard states at the
specified temperature.
• Always negative as it is exothermic
• E.g., C6H12O6 (g)+ 6 O2(g) → 6CO2(g) + 6 H2O(l); ∆ c H Θ = – 2802.0 kJ mol–1
2. Enthalpy of Atomization, ∆ a H Θ
• Enthalpy change on breaking one mole of bonds completely to obtain atoms in the gas
phase.
• E.g., H2(g) → 2H(g) ∆ a H Θ = 435.0 kJ mol–1

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 SPECIAL TUITION FOR PHYSICS CHEMISTRY & BIOLOGY

• For diatomic molecules, like dihydrogen (H2), the enthalpy of atomization is also the
bond dissociation enthalpy
3. Enthalpy of Neutralization (Δneut Hº)
• Enthalpy change when one mole of hydrogen ions (H+) is neutralized by one mole of
hydroxyl ions (OH-) in dilute aqueous medium to form water.
• For example: H+ (aq) + OH– (aq) →H2O (l) ; Δneut H = –57 kJ/mol
4. Standard Enthalpy of ionization (ΔionH0)
• Change in enthalpy when one mole of a weak electrolyte ionizes completely in its
solution at a constant temperature and under 1 bar pressure
• Example: HCN(aq) ⎯→ H+ (aq)+ CN–(aq) ΔionH = 43.7 kJ mol–1
5. Bond Enthalpy ∆ bond H Θ
• Enthalpy changes associated with breaking and making of chemical bonds.
• bond dissociation enthalpy: enthalpy change in when one mole of covalent bonds of
a gaseous covalent compound is broken to form products in gas phase
• E.g., Diatomic molecules, Cl2(g) → 2Cl(g) ; ∆ Cl−Cl H Θ = 242 kJ mol-1
• For Polyatomic Molecules, we use mean bond enthalpy of C – H bond
• CH4(g) → CH3(g)+H(g) ; ∆ bond H Θ = +427 kJ mol-1
• CH3(g) → CH2(g)+2H(g) ; ∆ bond H Θ = +439 kJ mol-1
• CH2(g) → CH (g)+3H(g); ∆ bond H Θ = +452 kJ mol-1
• CH(g) → C(g)+4H(g) ∆ bond H Θ = +347 kJ mol-1
• Therefore, CH4(g) → C(g)+4H(g); ∆ bond H Θ = 1665 kJ mol-1
6. Lattice Enthalpy
• Enthalpy change which occurs when one mole of an ionic compound dissociates into
its ions in gaseous state
• Born-Haber Cycle: Enthalpy diagram to determine indirectly the lattice enthalpies
of ionic compounds

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 SPECIAL TUITION FOR PHYSICS CHEMISTRY & BIOLOGY

7. Enthalpy of Solution, ∆ sol H Θ

• Enthalpy change when one mole of it dissolves in a specified amount of solvent.
• Enthalpy of solution at infinite dilution: enthalpy change observed on dissolving
the substance in an infinite amount of solvent when interactions between the ions (or
solute molecules) are negligible.
• Enthalpy of solution in water, ∆ sol H Θ = ∆ lattice H Θ + ∆ hyd H Θ

8. Enthalpy of Dilution, ∆ dil H Θ

• Enthalpy change associated with the addition of a specified amount of solute to the
specified amount of solvent at a constant temperature & pressure.
• It is the heat withdrawn from surroundings when additional solvent is added to
solution.
• Depend on enthalpy of solution, original concentration of the solution & amount of
solvent added.
• As more & more solvent is used, the enthalpy of solution approaches a limiting value,
i.e, value in infinitely dilute solution

SPONTANEITY

• Spontaneity (Latin spontaneus "willing, of one's free will) means ‘having the potential
to proceed without the assistance of external agency’.
• A spontaneous process is an irreversible process and may only be reversed by some
external agency
• E.g., ½ N2(g) + O2(g) → NO2(g); ∆ r H Θ = +33.2 kJ mol-1

Entropy, S

• Measure of degree of randomness or disorder of a system

• It is the energy unavailable to do work

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 SPECIAL TUITION FOR PHYSICS CHEMISTRY & BIOLOGY

• Entropy is a state function

• It is measured in J K-1 mol-1
• Temperature is the measure of average chaotic motion of particles in the system
• Standard entropy: entropy of a pure substance under standard conditions of pressure
and temperature.

Entropy change, ∆S

• Change in the disorder (entropy) within a system as the result of a chemical or

physical process.
q
• ∆S = rev
T
• ∆Stotal = ∆Ssystem + ∆Ssurrounding > 0
• When a system is in equilibrium, entropy is maximum & ∆S = 0.
q sys.rev
• For a reversible reaction, ∆Stotal =
T
• Entropy of different states of matter increases as you move from solid to liquid to gas
due to the increasing disorder between the molecules

Gibbs Energy

• It can be used to calculate maximum amount of work that may be performed by a

thermodynamically closed system at constant temperature and pressure.
• Gibbs function, G = H – TS
• Gibbs function, G is an extensive property and a state function

Derivation of Gibbs Free Energy Formula

• Since, G = H – TS …..(1) & H = U + PV ……. (2)

• Putting value of H in Equation 1, we get G = U + PV – TS
• Gibbs free energy changes can be written as ΔG = ΔU + Δ(PV) – Δ(TS)
• ΔT=0 and ΔP=0 if the change is done at the same temperature and pressure.
• ΔG = ΔU + PΔV – TΔS
• Here, ΔH = ΔU + PΔV
• ∴∆G=∆H-T∆S ; Gibbs equation
• T∆Stotal = T∆Ssys –∆Hsys

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 SPECIAL TUITION FOR PHYSICS CHEMISTRY & BIOLOGY

• ∆Hsys is the enthalpy change of a reaction; T∆Ssys is the energy which is not available
to do useful work.
• So ∆G is the net energy available to do useful work & is thus a measure of ‘free
energy’
• ∆G=∆H-T∆S <0
• If ∆G is negative (< 0), the process is spontaneous.
• If ∆G is positive (> 0), the process is non-spontaneous

Entropy and Second Law of Thermodynamics

• According to the second law of thermodynamics all spontaneous or natural processes

produce an increase in entropy of the universe.
• In exothermic reactions heat released by reaction increases disorder of surroundings
and overall entropy change is positive which makes the reaction spontaneous.

Absolute Entropy and Third Law of Thermodynamics

• The third law of thermodynamics states that entropy of any pure crystalline substance
approaches zero as the temperature approaches absolute zero.
• But practical evidences have shown that entropy of solutions and super cooled liquids
is not zero at 0 K.

GIBBS ENERGY CHANGE AND EQUILIBRIUM

• 
→ C + D ; ∆rG = 0
For a reaction A + B ←

0 = ∆rG + RT ln K
or ∆rG = – RT ln K
• or ∆rG = – 2.303 RT log K

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 SPECIAL TUITION FOR PHYSICS CHEMISTRY & BIOLOGY

∆ r G Θ =∆H − T∆ rSΘ =−2.303RT log K =−2.303RT log

[C][ D]
[ A ][ B]

• For endothermic reactions, value of ∆ r H Θ may be large and positive

• For exothermic reactions, value of ∆ r H Θ may be large and negative

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