General Chemistry (CHEM F111)

Lecture-17
22/02/2024
RECAP
Thermodynamics: Terms and Definitions
 Work, Heat and Energy
• Work and heat are modes of transfer of
energy, not the forms of energy.
•Work (w) is done to achieve motion against
opposing force.
•The energy of a system is its capacity to do work.
• Heat (q) generally results in temperature
difference between system and its surroundings.

•Temperature (T) defines the state of a system

and determines the direction of flow of heat.
Isothermal Reversible work: (A perfect gas)

pdV

Expansion: Vf > Vi , W < 0

Compression: Vf < Vi, W > 0

Irreversible work:
w = -pf (Vf – Vi )
Molecular interpretation of Work and Heat

Uniform
motion

Random
motion
Today’s Topic
First law of thermodynamics and First law
quantities
 Heat Capacities
The heat capacity of a closed system for an infinitesimal process,
Cpr = dqpr/dT. It depends on nature of process. At constant P, CP =
dqP/dT. At constant V, CV = dqV/dT. (Strictly speaking applicable
for reversible process).
Heat capacity is an extensive property, to express as intensive
property we determine:
For a one-phase system of mass m, specific heat capacity,
Cs = CP /m or CV/m (J/K/g).

For a pure substance, molar heat capacity, CP,m = CP/n

or CV,m = CV/n (J/K/mol).
Assuming that heat capacity remains constant in a finite
temperature range T, C = q/T.
Measurement: C = IVt/T ( I = current, V=voltage, t = time)
 The Measurement of Heat
Measurement of energy transferred as heat in a chemical
reaction or in a physical process using calorimeter.

The heat capacity of a calorimeter, C = q/T = IVt/T,

where q is energy supplied as heat and T is change in temperature
of the water bath. C is called calorimeter constant.

Therefore, energy absorbed or released by a system as heat in a

chemical reaction or in a physical process, q = CT .
T  = change in temperature of bath after reaction/physical process
has taken place.
 Internal Energy, U
• Internal energy U is a state function which represents
the sum total of all molecular energies (translational,
rotational, vibrational) and potential energies of
interaction of the molecules in the system.
• U is an extensive function. For a closed system, U =
U(T,V)
• The molar internal energy Um is intensive. It is
difficult to measure total molecular energy of a sample
i.e. internal energy, U. But changes in internal energy
U can be measured.
• For a closed system, U = q + w
 State Function

Path independent. Depends only

on the current state of the system.

Internal energy (U) is a state function

Work (w), heat (q) are path dependent functions

 First Law of Thermodynamics

Internal energy changes due to

transfer of energy as heat or
work or both heat and work
for a closed system.

Therefore, U = w + q for a
closed system.

• w  0 and q  0 when energy is transferred to the system.

• w  0 and q  0 when energy leaves the system in the form
of work or heat.
Work done on the system +ve ; Work done by the system –ve
 First Law for Closed Systems
In general, both w and q may be nonzero for a
process. Then
U = q + w
For an infinitesimal change,
dU = q + w
• q and w are path dependent while U is not.
• q and w both taken as positive when energy
transferred to system from surroundings.
• q and w both measured in J (= kgm2/s2)
 First Law – different versions
➢ If a system is enclosed by an adiabatic, impermeable
and rigid wall and no other non-expansion work is
done on it, (in other words the system is isolated) then
U = 0, or
U = Constant (Isolated)
“The internal energy of an isolated system is constant” - A
statement of First law of thermodynamics.
➢ U = wadia (adiabatic process, q = 0, closed system)
What is the significance? Under adiabatic condition,
work done will always be same whatever path it takes !
➢ For a closed system at constant volume and no
non-expansion work, U = qv
Measurement of U
The change in internal energy of a chemical
reaction can be determined by performing the
reaction in a bomb calorimeter (constant volume).

U = qv
Reversible isothermal process for a perfect
gas (Closed system)

Perfect gas: U = U(T)

Isothermal process, so U = 0
First law: q = - w = - (-nRT)ln(Vf/Vi)

As reversible process, pdV

Perfect gas: H = H(T)

Isothermal process, so H = 0
Heat Capacity at constant volume and temperature
variation of internal energy

•Energy absorbed/released as heat by a closed system at

constant volume, dq is equal to internal energy change, dU
of the system. i.e. dU = dq at constant volume (no non-
expansion work).

Heat capacity At constant, V

at constant volume,
CV = dqv/dT. Therefore, CV = (U/T)V, closed system in
eqm., P-V work only.
Heat Capacity at constant volume and internal energy
change of a perfect gas

CV = (U/T)V, closed system in eqm., P-V work only.

For a perfect gas in a closed system, U = U(T)
Therefore, CV = dU/dT or dU = CVdT
[It follows, Cv = Cv(T) for a perfect gas]
Tf
For a finite change, U =  CV dT
Ti

When CV is independent of temperature then,

U = CV(Tf – Ti) i.e. U = CV T
 Heat Transfer
Can one change the internal energy of a system
without performance of work? If yes, how?
By placing the system in thermal contact with a system
at a higher temperature
U = q (when w = 0)
This mode of energy transfer is called heat transfer,
denoted by q.
Process in which system absorbs heat is endothermic,
one in which system releases heat is exothermic
 Heat And Enthalpy
The energy supplied as heat to a system or released
by a system at constant pressure is equal to change
in another thermodynamic property called
ENTHALPY which is defined as, H = U + pV
It is a state function and an extensive property like
U and V.
Molar enthalpy Hm is an intensive property like Um,
p and Vm
Hm = Um + pVm = Um + RT for a perfect gas.
 Heat And Enthalpy
Since H = U + PV
Therefore dH = dU + PdV + VdP
dU = dq + dW = dq –PexdV (when work is
expansion and no non-expansion work).
dH = dq –PexdV + PdV + VdP
For a system open to atmosphere or in mechanical
equilibrium with surroundings, P = Pex
Therefore, dH = dq –PexdV + PexdV + VdP
i.e., dH = dq + VdP
 Heat And Enthalpy

If heating occurs at constant pressure, dP = 0

Therefore, dH = dq , at constant pressure

or, H = qp , at constant pressure

Therefore, if ‘q’ kJ of energy is supplied as heat to

a system which is free to change its volume at
constant pressure → the enthalpy increases by ‘q’
kJ regardless of how much energy is used by doing
work.
 Heat And Enthalpy

For an endothermic reaction (q0) taking place at

constant pressure H 0.

For an exothermic reaction (q0) taking place at

constant pressure H0.
Heat capacity at constant pressure and temperature
variation of enthalpy
Energy absorbed/released as heat by a closed
system at constant pressure, dq, is equal to
enthalpy change dH of the system (no non-
expansion work).
Therefore, dH = dqP
Heat capacity
at constant pressure
CP = dqp/dT or CP = (H/T)P, closed system in
eqm., PV work only
Heat capacity at constant pressure and enthalpy
change of a perfect gas

CP = (H/T)P, closed system in eqm., PV work only

For a perfect gas in a closed system, H = U+PV = U+
nRT. Therefore, for a perfect gas, H = H(T)
Therefore, Cp = dH/dT or dH = CpdT
[It follows, Cp = Cp(T) for a perfect gas]
Tf
For a finite change, H =  CP dT
Ti
When CP is independent of temperature then,
H = CP(Tf – Ti) i.e. H = CP T
 Constant pressure heating or cooling
CP = dqp/dT
dqp = dH = CP dT
Tf
For a finite change: H =  CP dT
Ti

or, H = CP T when CP is independent in

this temperature range.
 Constant volume heating or cooling
CV = dqv/dT
Or, dqv = dU = CVdT
Tf
For a finite change, U =  CV dT
Ti

When CV is independent of temperature then,

U = CV(Tf – Ti) i.e. U = CV T
Thermochemistry (Self Study, T1-6th edition:3.1-3.7 )

• Role of Enthalpy in Chemistry

•The Enthalpy of Phase transition

•Enthalpies of combustion

•Standard Enthalpies of formation

•Variation of reaction Enthalpy with temperature:

Kirchhoff’s law
Second law of Thermodynamics

Second law has many forms,

but it originates from the same
principle of

Directional constraint
of natural processes
 Natural / Spontaneous Processes
“proceed towards equilibrium and take place in a
particular direction”
Example:

Fluid always flows from a higher elevation to a

lower elevation spontaneously
Heat always flows from high temperature to low
temperature (spontaneous cooling)
Materials always diffuse from high concentration
to low concentration
Reverse of this never happens, without any external source
29
Natural / Spontaneous Processes

Spontaneous
Change
↕
disorderness

In either direction,
the process is
consistent with the
First Law.
 Natural / Spontaneous Processes

Blocks in thermal
contact, but
T TL
adiabatically H
isolated from the
rest of the
universe

T T

Dispersal of energy
Second law of Thermodynamics
 Natural / Spontaneous Processes

Spontaneous Processes:
Matter tends to become disordered.
Energy tends to become disordered.
Disorder – “Mixing” or “ Spreading”.
More disorder – Greater probability, More
microstates (later)