Thermodynamics The study of Heat and Work and State Functions

Dr. Tarek T. Ali

E-mail: Catalysa98@msn.com Mobile: 0569570912

THERMOCHEMISTRY

Session Objectives

1. Zero-th law 2. Internal energy 3. Work

4.First law of thermodynamics

5. Course assignment 1

Zeroth law (Law of thermal equilibrium) When two systems are in thermal equilibrium with a third system, then they in turn are in thermal equilibrium with each other (A)
(B)

Thermal equilibrium
Thermal equilibrium

(B)
(C)

(A)

Thermal equilibrium (C)

Potential & Kinetic Energy

Potential energy: energy a motionless body has by virtue of its position.

Potential Energy on the Atomic Scale

Positive and negative particles (ions) attract one another. Two atoms can bond As the particles attract they have a lower potential energy

Potential & Kinetic Energy

Kinetic energy:
energy of motion Translation

Potential & Kinetic Energy

Kinetic energy: energy of motion

rotate vibrate translate

Internal Energy

Energy stored within a substance of a system

E = Ee + Ev + E r

internal energy or intrinsic energy

PE + KE = Internal energy (E or U)
Internal Energy of a chemical system depends on

number of particles type of particles temperature

Internal Energy

The higher the T the higher the internal energy So, use changes in T (T) to monitor changes in E (E).

Internal Energy

Actual (absolute) value can not be measured change in internal energy (E) can be measured It is an extensive property. ()

Internal energy is a state function

For a cyclic process, E = 0

Work

Work done = Force Displacement

W = P (V2 V1) (At constant pressure) W = PV
where, W = work done

W = ve, work done by the system (expansion)

W = +ve, work done on the system (contraction)

Work
Work done in isothermal reversible expansion of an ideal gas
Suppose an ideal gas is enclosed in a cylinder fitted with a weightless and frictionless piston and the cylinder is not insulated. Under equilibrium condition, Pg (i.e. gas pressure) = Pext (i.e. external pressure) If the external pressure is decreased by very small amount (dP), then the gas will expand by dV amount to reestablish the equilibrium and the gas pressure also becomes (Pg dP), i.e. equal to the external pressure (Pext).

Pext

Pext dP
dv

Pg

Pg

Work
Work done in this isothermal reversible process in each step is,

W = (Pext dP)dV

Pext dV
Hence, the total work done in an isothermal expansion from volume V1 to V2 is
V2 v1

Wrev

PdV

Since PV = nRT

Work
Wrev
V2 V1

nRT dV V

Wrev

V2 nRT ln V1

Wrev = 2.303 nRT log

1 Since P V

V2 V1

Wrev = 2.303 nRT log

P1 P2

Work done in irreversible isothermal expansion Free expansion Pext = 0, i.e. work done is zero when gas expands in vacuum. Intermediate expansion Pext < Pg. So, the work done when volume changes from V1 to V2 is Wirr = Pext(V2 V1)

First Law of Thermodynamics

Energy is conserved!
Energy can neither be created nor destroyed
If E1 is the initial internal energy of the system, q is the heat absorbed, w is the work done on the system. Then according to the first law of thermodynamics the final internal energy E2 of the system is given by
heat energy transferred

E2 = E1 + q + w
E2 E1 = q + w

E = q + w
energy change

work done by the system

heat transfer in (endothermic), +q

heat transfer out (exothermic), -q

SYSTEM

E = q + w

w transfer in (+w)

w transfer out (-w)

If work is done by the system, (in case of expansion) w = - Pv

E = q - Pv q = E + Pv

a. During isothermal expansion

E = 0

q = Pv
b. In case of adiabatic process, q = 0

E = - Pv = +w E = +w

c. In case, the process is carried out at constant volume

V = 0 PV = 0 or w = 0 qV = E
Quantity of heat supplied at constant volume, qv is equal to increase in the internal energy of the system.

Course Assignment (1)