Thermodynamics-(Basics)

Thermodynamics-(Physics)
 Thermodynamics:- It is the branch of physics which deals with process involving heat,
work and internal energy. Thermodynamics is concerned with macroscopic behavior rather
than microscopic behavior of the system.
 Basic Terminology:-
System Part of the universe under investigation.

Open System A system which can exchange both energy and matter
with its surroundings.
Closed System A system which permits passage of energy but not
mass, across its boundary.
Isolated system A system which can neither exchange energy nor
matter with its surrounding.
Surroundings Part of the universe other than system, which can
interact with it.
Boundary Anything which separates system from surrounding.

State variables The variables which are required to be defined in order

to define state of any system i.e. pressure, volume,
mass, temperature, surface area, etc.
State Functions Property of system which depend only on the state of
the system and not on the path.
Example: Pressure, volume, temperature, internal
energy, enthalpy, entropy etc.
Intensive properties Properties of a system which do not depend on mass
of the system i.e. Temperature, pressure, density,
concentration,
Extensive properties Properties of a system which depend on mass of the
system i.e. Volume, energy, enthalpy, entropy etc.
Process Path along which state of a system changes.

Isothermal process Process which takes place at constant temperature

Isobaric process Process which takes place at constant pressure

Isochoric process Process which takes place at constant volume.

Adiabatic process Process during which transfer of heat cannot take

place between system and surrounding.
Cyclic process Process in which system comes back to its initial state
after undergoing series of changes.
Reversible process Process during which the system always departs
infinitesimally from the state of equilibrium i.e. its
direction can be reversed at any moment.

 Kinetic Energy:- Energy possessed by the atoms or molecules by virtue of their

motion is called kinetic energy.
 Internal Energy (ΔU):- Sum total of kinetic and potential energies of atoms/molecules
constituting a system is called the internal energy of the system.
(a) ΔU is taken as positive if the internal energy of the system increases.
(b) ΔU is taken as negative if the internal energy of the system decreases.
 Heat:- Heat is the part of internal energy which is transferred from one body to another an
account of the temperature difference.
 Work:- Work is said to be done when a force acting on a system displaces the body in its
own direction.
dW = Fdx = PdV
W = P(V f -V i )
(a) If the gas expands, work is said to be done by the system. In this case V f > V i ,
therefore, W will be positive.
(b) If the gas is compressed, work is said to be done on the system. In this case V f < V i ,
therefore, work done is negative.
 Thermodynamic variables or parameters:- The thermodynamic state of system can be
determined by quantities like temperature (T), volume (V), pressure (P), internal energy
(U) etc. These quantities are known as thermodynamic variables, or the parameters of the
system.
 Equation of state:- A relation between the values of any of the three thermodynamic
variables for the system, is called its equation of state.

Equation of state for an ideal gas is PV = RT

 Equilibrium of a system:- A system is said to be in equilibrium if its macroscopic

quantities do not change with time.
 Relation between joule and calorie:- 1 joule = 4.186 cal
 First law of thermodynamics:- If the quantity of heat supplied to a system is capable of
doing work, then the quantity of heat absorbed by the system is equal to the sum of the
increase in the internal energy of the system, and the external work done by it.

dQ = dU+dW
 Thermodynamic Process:- A process by which one or more parameters of
thermodynamic system undergo a change is called a thermodynamic process or a
thermodynamic change.
 (a) Isothermal process:- The process in which change in pressure and volume takes
place at a constant temperature, is called a isothermal change. It may be noted that in
such a change total amount of heat of the system does not remain constant.
(b) Isobaric process:- The process in which change in volume and temperature of a
gas take place at a constant pressure is called an isobaric process.
(c) Isochoric process:- The process in which changes in pressure and temperature
take place in such a way that the volume of the system remains constant, is called
isochoric process.
(d) Adiabatic process:- The process in which change in pressure and volume and
temperature takes place without any heat entering or leaving the system is called
adiabatic change.
(e) Quasi-static process:- The process in which change in any of the parameters take
place at such a slow speed that the values of P,V, and T can be taken to be, practically,
constant, is called a quasi-static process.
(f) Cyclic process:- In a system in which the parameters acquire the original values,
the process is called a cyclic process.
(g) Free expansion:- Such an expansion in which no external work is done and the
total internal energy of the system remains constant is called free expansion.
 Reversible isothermal and adiabatic curve:-

 Application of first law of thermodynamics:-

(a) Cooling caused in adiabatic process:- dT = PdV/C v
(b) Melting:- dU = mL f
(c) Boiling:- dU = mL v – P(V f -V i )
(d) Mayer’s formula:- C p - C v = R
 Specific heat capacity of gases:- Specific heat capacity of a substance is defined as the
amount of heat required to raise the temperature of a unit mass of substance through 1ºC.
(a) Specific heat capacity at constant volume (c v):- Specific heat capacity at
constant volume is defined as the amount of heat required to raise the temperature of
1 g of the gas through 1ºC keeping volume of the gas constant.
 Molar specific heat capacity, at constant volume (C v ), is defined as the amount of heat
required to raise the temperature of 1 mole of gas through 1ºC keeping its volume
constant.
C v = Mc v
(b) Specific heat capacity at constant pressure (c p ):- Specific heat capacity, at
constant pressure, is defined as the amount of heat required to raise the temperature of
1 g of gas through 1ºC keeping its pressure constant.
Gram molecular specific heat capacity of a gas (C p ), at constant pressure, is defined as
the amount of heat required to raise the temperature of 1 mole of the gas through
1ºC keeping its pressure constant.
C p = Mc p
 Difference between two specific heat capacities – (Mayer’s formula):-
(a) C p - C v = R/J
(b) For 1 g of gas, c p - c v = r/J
(c) Adiabatic gas constant, γ = C p / C v = c p / c v
 Relation of C v with energy:-
C v = 1/m (dU/dT)
(a) Mono-atomic gas (3 degree of freedom):-
Total energy, U = mN 3 [(1/2) KT], Here m is the number of moles of the gas and N is
the Avogadro’s number.
C v = (3/2) R
C p = (5/2) R
γ = C p / C v = 5/3 = 1.67
(b) Diatomic gas:-
At very low temperature, Degree of Freedom (DOF) = 3
U = (3/2) mRT
C v = (3/2) R, C p = (5/2) R
γ= C p / C v = 5/3 = 1.67
At medium temperature, DOF = 5
U = (5/2) mRT
C v = (5/2) R, C p = (7/2) R
γ = C p / C v = 7/5 = 1.4
At high temperature, DOF = 7
U = (7/2) mRT
C v = (7/2) R, C p = (9/2) R
γ = C p / C v = 9/7 = 1.29
γ
 Adiabatic gas equation:- PV = Constant
γ-1
(a) Equation of adiabatic change in terms of T and V:- TV = Constant
γ 1-γ
(b) Equation of adiabatic change in terms of P and T:- T P = Constant
 Comparison of slopes of an isothermal and adiabatic:-
 (a) Slope of isothermal:- dP/dV = -P/V
(b) Slope of adiabatic:- dP/dV = -γP/V
(c) Adiabatic gas constant:- γ = C p /C v
As, C p >C v , So, γ>1
This signifies that, slope of adiabatic curve is greater than that of isothermal.
 Slope on PV diagram:-
(a) For isobaric process: zero
(b) For isochoric process: infinite
 Work done for isobaric process:- W = P(V 2 -V 1 )

 Work done for isochoric process:- W = 0

 Work done in isothermal expansion and compression:-
?W = 2.3026 RT log 10 V f /V i (isothermal expansion)
W = - 2.3026 RT log 10 V f /V i (isothermal compression)
 Work done during an adiabatic expansion:-

1-γ 1-γ
W = K/1-γ [V f – Vi ] = 1/1-γ [P 2 V 2 -P 1 V 1 ] = R/1- γ [T 2 -T 1 ]
 Adiabatic constant (γ):- γ = C p /C v = 1+2/f, Here f is the degrees of freedom.
 Work done in expansion from same initial state to same final volume:-
 W adiabatic < W isothermal < W isobaric
 Work done in compression from same initial state to same final volume:-
W adiabatic < W isothermal < W isobaric
 Reversible process:- It is a process which can be made to proceed in the reverse
direction by a very slight change in its conditions so that the system passes through the
same states as in direct process, and at the conclusion of which the system and its
surroundings acquire the initial conditions.
Example:- All isothermal and adiabatic process when allowed to proceed slowly, are
reversible, provided there is no loss of energy against any type of resistance. Friction,
viscosity are other examples.
 Irreversible process:- A process which cannot be made to be reversed in opposite direction
by reversing the controlling factor is called an irreversible process.
Example:-
(a) work done against friction
(b) Joule’s heating effect
(c) Diffusion of gases into one another
(d) Magnetic hysteresis
 Heat engine:- It is a device used to convert heat into mechanical energy
(a) Work done, W = Q 1 -Q 2
(b) Efficiency:- Efficiency η of an engine is defined as the fraction of total heat,
supplied to the engine which is converted into work.
η= W/ Q 1 = [Q 1 - Q 2 ]/ Q 1 = 1-[Q 2 /Q 1 ]
 Carnot engine – Carnot’s reverse cycle:-
(a) First stroke (isothermal expansion):- W 1 = RT 1 log e [V 2 /V 1 ]
(b) Second stroke (adiabatic expansion):- W 2 = R/γ-1 [T 1 -T 2 ]
(c) Third stroke (isothermal compression):- W 3 = RT 2 log e V 3 /V 4
(d) Fourth stroke (adiabatic compression):- W 4 = R/γ-1 [T 1 -T 2 ]
(e) Total work done in one cycle, W = W 1 + W 2 + W 3 + W 4 = R (T 1 -T 2 ) log e (V 2 /V 1 )
 Efficiency of Carnot engine:- Efficiency η of an engine is defined as the ratio between
useful heat (heat converted into work) to the total heat supplied to the engine.
η = W / Q 1 = [Q 1 - Q 2 ]/ Q 1 = 1-[Q 2 /Q 1 ] = 1- T 2 /T 1
 Second law of thermodynamics:-
(a) Clausius statement:- Heat cannot flow from a cold body to a hot body without the
performance of work by some external agency.
(b) Kelvin’s statement:- It is impossible to obtain a continuous supply of energy by
cooling a body below the coldest of its surroundings.
(c) Planck’s statement:- It is impossible to extract heat from a single body and convert
the whole of it into work.
 Refrigerator:- It is a device which is used to keep bodies at a temperature lower than that
of surroundings.
 Coefficient of performance (β):- Coefficient of performance of a refrigerator is defined as
the amount of heat removed per unit work done on the machine.
β = Heat removed/work done = Q 2 /W = Q 2 /[Q 1 - Q 2 ] = T 2 /[T 1 - T 2 ]
Coefficient of performance of a refrigerator is not a constant quantity since it depends
upon the temperature of body from which the heat is removed.
For a perfect refrigerator, W = 0 or Q 1 = Q 2 or β =∞

2
Mean free path:- λ= 1/√2πd ρ n
Here ρ n = (N/V) = number of gas molecules per unit volume
d = diameter of molecules of the gas.
 Heat added or removed:-
 (a) For isobaric process:- Q = n C p ΔT
(b) For isochoric process:- Q = n C v ΔT
(c)For isothermal process:- Q = nRT log e (V 2 /V 1 )
(d) For adiabatic process: Q = 0
 Change in internal energy:-
(a) For isobaric process, ΔU = n C p ΔT
(b) For isobaric process, ΔU = n C v ΔT
(c) For isothermal process, ΔU = 0
(d) For adiabatic process, ΔU = -W = [nR (T 2 -T 1 )]/(γ-1)
 Mixture of gases:- n = n 1 +n 2
M = n 1 M 1 +n 2 M 2 / n 1 + n 2 = N 1 m 1 +N 2 m 2 /N 1 +N 2

and

 Enthalpy (H):-
(a) H = U+PV
(b) At constant pressure:-
dH = dU + pdV
(c) For system involving mechanical work only:-
dH = Q P (At constant pressure)
(d) For exothermic reactions:-
dH is negative
(e) For endothermic reactions:-
dH is positive
 Relation between dH and dU:-
dH = dU + dn g RT
Here, dn g = (Number of moles of gaseous products - Number of moles of gaseous
reactants)

Thermodynamics-(Chemistry)

Basic Terminology:
Terms Explanation

System Part of the universe under investigation.

Open System A system which can exchange both energy and matter with
its surroundings.
Closed System A system which permits passage of energy but not mass,
across its boundary.
Isolated system A system which can neither exchange energy nor matter
with its surrounding.
Surroundings Part of the universe other than system, which can interact
with it.
Boundary Anything which separates system from surrounding.

State variables The variables which are required to be defined in order to

define state of any system i.e. pressure, volume, mass,
temperature, surface area, etc.
State Functions Property of system which depend only on the state of the
system and not on the path.
Example: Pressure, volume, temperature, internal energy,
enthalpy, entropy etc.
Intensive properties Properties of a system which do not depend on mass of the
system i.e. temperature, pressure, density, concentration,
Extensive properties Properties of a system which depend on mass of the
system i.e. volume, energy, enthalpy, entropy etc.
Process Path along which state of a system changes.

Isothermal process Process which takes place at constant temperature

Isobaric process Process which takes place at constant pressure

Isochoric process Process which takes place at constant volume.

Adiabatic process Process during which transfer of heat cannot take place
between system and surrounding.
Cyclic process Process in which system comes back to its initial state after
undergoing series of changes.
Reversible process Process during which the system always departs
infinitesimally from the state of equilibrium i.e. its direction
can be reversed at any moment.
Irriversible Process This type of process is fast and gets completed in a single
step. This process cannot be reversed. All the natural
processes are of this type

Heat, energy and work:

Heat (Q):
 Energy is exchanged between system and surround in the form of heat when they are at
different temperatures.
 Heat added to a system is given by a positive sign, whereas heat extracted from a system
is given negative sign.
 It is an extensive property.
 It is not a state function.
Energy:
 It is the capacity for doing work.
 Energy is an extensive property.
 Unit : Joule.
Work (W):
 Work = Force × Displacement i.e. dW = Fdx
 Work done on the system is given by positive sigh while work done by the system is given
negative sign.
 Mechanical Work or Pressure-Volume Work: work associated with change in volume of a
system against an external pressure.
 Work done in reversible process: W=

W = – 2.303 nRT log v2 /v1 = –2.303 nRT log p 1 /p 2

 Wok done in isothermal reversible contraction of an ideal gas:
?W = – 2.303 nRT log v 2 /v1 = –2.303 nRT log p 1 /p 2
 Unit : Joule.
Internal Energy (E or U):
 Sum of all the possible types of energy present in the system.

 ΔE = heat change for a reaction taking place at constant temperature and volume.

 ΔE is a state function.

 It is an extensive property.

 Value of ΔE is -ve for exothermic reactions while it is +ve for endothermic reactions.

First Law of Thermodynamics:

Energy can neither be created nor destroyed although it can be converted from one form
to another.
or
Energy of an isolated system is constant.
Mathematical Expression
Heat observed by the system = its internal energy + work done by the system.
i.e. q = dE + w
For an infinitesimal process

dq = dE + dw
Where, q is the heat supplied to the system and w is the work done on the system.

For an ideal gas undergoing isothermal change ΔE =0.

so q= -w.
 For an isolated system, dq=0
so, dE = - dw
 For system involving mechanical work only
ΔE = q - pdV
 At constant volume i.e. isochoric process
ΔE = q v
 For Isothermal Process
ΔE = 0
or
q = - pdV =-W
 For adiabatic process
?q = 0

or

ΔE = W
Enthalpy (H):
H = E+PV

At constant pressure:

dH = dE + pdV
For system involving mechanical work only

dH = QP (At constant pressure)

For exothermic reactions:

dH = -ve

For endothermic reactions:

dH = +ve

Relation between dH and dE:

dH = dE + dn g RT
Where,

dn g = (Number of moles of gaseous products - Number of moles of gaseous reactants)

Heat capacity:
 Amount of heat required to rise temperature of the system by one degree.
C = q / dT
 Specific heat capacity: Heat required to raise the temperature of 1 g of a substance by one
dgree.
C s = Heat capacity / Mass in grams
 Molar heat capacity: Heat required to raise the temperature of 1 g of a substance by one
dgree.
C m = Heat capacity / Molar mass.
 Heat capacity of system at constant volume:
Cv = (dE/dT) v
 Heat capacity of system at constant pressure:
C p = (dE/dT) p
Cp – Cv = R
 Variation Of Heat Of Reaction With Temperature:
dC P = (dH 2 - dH 1 )/(T 2 -T 1 ) & dC V = (dE 2 - dE 1 )/(T 2 -T 1
 Bomb Calorimeter:
?
Heat exchange = Z × ΔT

Z–Heat capacity of calorimeter system

ΔT– Rise in temp.

Heat changes at constant volumes are expressed in ΔE and Heat changes at constant

pressure are expressed in dH.

Enthalpies of Reactions:
Enthalpies Definitions Example

Enthalpy of Enthalpy change when one H 2 (g) + 1/2O 2 (g) → 2H 2 O(l),

Formation mole of a given compound is Δ f H = –890.36 kJ / mol
formed from its elements
Enthalpy of Enthalpy change when one CH 4 + 2O2 (g) →CO2 + 2H 2 O(l),
Combustion mole of a substance is burnt Δ comb H = –890.36 kJ / mol
in oxygen.
Enthalpy of Enthalpy change when one H + (aq) + OH – (aq) → H 2 O(l)
Neutralization equivalent of an acid is Δ neut H = –13.7 kcal
neutralized by a base in dilute
solution.
Enthalpy of Enthalpy change when a salt CuSO 4 (s) + 5H 2 O (l) → CuSO 4 5H 2 O,
Hydration combines with the required Δ hyd H° = –18.69 kcal
number of moles of water to
form specific hydrate.
Enthalpy of Enthalpy change when one C
Transition mole of a substance is (graphite) → C(diamond), ΔtransH°
transformed from one = 1.9 kJ/mol
allotropic form to another
allotropic form.
Enthalpy of Enthalpy change when one CO 2 (S) → CO 2 (g)
Sublimation mole of a solid substance Δt f usH° = 6.00 kJ/mol
sublime at constant temp. and
1 bar pressure
Enthalpy of Enthalpy change when one H 2 O(S) → H 2 O (l)
fusion mole of a solid melts Δt sub H° = 73.00 kJ/mol
Hess’s Law of constant heat summation:
?The total enthalpy change of a reaction is the same, regardless of whether the reaction
is completed in one step or in several steps.

According to Hess’s law: ΔH = ΔH 1 + ΔH 2

Born–Haber Cycle:

Applying Hess’s law we get

ΔH 1 + 1/2 ΔH 2 + ΔH 3 + ΔH 4 + ΔH 5 = ΔH f (MX) (Lattice energy)

Lattice energy: The change in enthalpy that occurs when 1 mole of a solid crystalline
substance is formed from its gaseous ions.
Second law of thermodynamics
Statement:
It is impossible to take heat from a hot reservoir and convert it completely into work by a
cyclic process without transferring a part of it to a cold reservoirs.
Mathematically:
 ΔS = q rev /T
Where,
ΔS is entropy change.
 Entropy is the degree of randomness thus it increases with increase in randomness
of particles of the system i.e. ΔS is positive for melting of ice.
 At equilibrium, ΔS = 0
 For a spontaneous process, ΔS > 0
 Entropy change in an isothermal reversible expansion of a gas

 Spontaneous Processes: These type of physical and chemical changes occur of its
own under specific circumstances or on proper initiations. For example: Flow of liquids
from higher to lower level.

Gibbs free energy(ΔG):
 ΔG = ΔH - TΔS

 ΔG = nRT ln K eq
 ΔG = nFE cell
 At equilibrium, ΔG = 0

 For spontaneous process, ΔG < 0

Bond Energies:
Average amount of energy required to break one mole bonds of that type in gaseous
molecules.

H–OH(g) → 2H(g) + ½O(g) ΔH = 498 kJ

O–H(g) → H 2 (g) + ½O 2 (g) ΔH = 430 Kj

ΔH O–H = (498 + 430)/2 = 464 kJ mol –1
 Efficiency of a heat engine (carnot cycle):
W = R (T 2 – T 1 ) ln v2 /v 1
q 2 = RT 2 ln v 2 /v 1

Efficiency (h). h =