Chemical Engineering

Thermodynamics – I
ChE–301
Aqeel Ahmad TAIMOOR
 Class Objectives
 Understand Potential and Kinetic Energy

 Understand the concept of Internal Energy

 Understand the difference between Heat and Work

 Understand the Conventions and Terminology used in energy

balance

 Understand and apply the first Law of Thermodynamics to closed

systems

 Understand the difference between state and non-state functions

 Understand the difference between Chemical and mechanical

Equilibrium

 Apply Phase rule at Equilibrium

 Energy
 Ability of a system to do work is termed as energy.

 Kinetic Energy

 dW = F dl = ma dl = m du/dt dl = m du dl/dt

 dW = mu du

 Integrating W or EK = Δ(1/2mu2)

 Potential Energy

 dW = Fdl = mg dh and after integration EP = mgh

 Law of Energy conservation

 Class Objectives
 Understand Potential and Kinetic Energy

 Understand the concept of Internal Energy

 Understand the difference between Heat and Work

 Understand the Conventions and Terminology used in energy

balance

 Understand and apply the first Law of Thermodynamics to closed

systems

 Understand the difference between state and non-state functions

 Understand the difference between Chemical and mechanical

Equilibrium

 Apply Phase rule at Equilibrium

 Internal Energy

 Joule’s Experiment (Heat capacity)

 Internal Energy U
 Energy of the molecules
 Absolute values of Internal Energy is unknown

 However only change in internal energy can be

determined
 Class Objectives
 Understand Potential and Kinetic Energy

 Understand the concept of Internal Energy

 Understand the difference between Heat and Work

 Understand the Conventions and Terminology used in energy

balance

 Understand and apply the first Law of Thermodynamics to closed

systems

 Understand the difference between state and non-state functions

 Understand the difference between Chemical and mechanical

Equilibrium

 Apply Phase rule at Equilibrium

 Heat and Work
 Heat and work are different forms of energy, both have
same units!

 Heat and work are just two different ways of transferring

energy

 Heat is the transfer of thermal energy between systems

 Work is the transfer of mechanical energy between

systems

 All the work can be converted to heat but inverse is not

true!!
 Class Objectives
 Understand Potential and Kinetic Energy

 Understand the concept of Internal Energy

 Understand the difference between Heat and Work

 Understand the Conventions and Terminology used in energy

balance

 Understand and apply the first Law of Thermodynamics to closed

systems

 Understand the difference between state and non-state functions

 Understand the difference between Chemical and mechanical

Equilibrium

 Apply Phase rule at Equilibrium

 Terminology
 SYSTEM: Any thing under
consideration

 BOUNDARY: The hypothetical limit

defining the system

 SURROUNDINGS: Everything
external to system are surroundings

 Closed (constant matter) and open

(matter is not constant) system
 Terminology
 Steady state: No net change in properties of the system
with time

 Thermodynamic cycle: The sequence of processes that

begins and ends at same state

 Heat: Q, Work: W, Internal Energy: U

 Intensive properties: do not depend on the mass of

system

 Extensive properties: depend on the mass of system

 Terminology
 Equilibrium: Balance because of equality of opposing
forces

 Quasi-equilibrium : Apparent equilibrium processes in

one direction equal those acting in the reverse direction

 Heat: Q, Work: W, Internal Energy: U

 Convention
 Heat added to system = +ive

 Work done on the system = +ive

 Heat removed from system = -ive

 Work done by system = -ive

 Class Objectives
 Understand Potential and Kinetic Energy

 Understand the concept of Internal Energy

 Understand the difference between Heat and Work

 Understand the Conventions and Terminology used in energy

balance

 Understand and apply the first Law of Thermodynamics to closed

systems

 Understand the difference between state and non-state functions

 Understand the difference between Chemical and mechanical

Equilibrium

 Apply Phase rule at Equilibrium

First Law of Thermodynamics
Energy cannot be created nor
destroyed
However Energy can take different
forms and can be transferred from one
body to another
First Law of Thermodynamics
 First Law is just the energy balance

 Energy in = Energy out + accumulated energy

 (For closed system)

 δQ +δW = dU + d(P.E) + d(K.E)

 δQ + δW = dU

 Δenergy of the surrounding = Δenergy of the system

 Problem
Water flows over a waterfall 100 m in height. Take 1 kg of
the water as the system, and assume that it does not
exchange energy with its surroundings.

1. What is the potential energy of the water at the top of

the falls with respect to the base of the falls?

2. What is the kinetic energy of the water just before it

strikes bottom?

3. After the 1 kg of water enters the stream below the falls,

what change has occurred in its state?
Problem Schematic
 Problem
An elevator with a mass of 2500 kg rests at a level of 10 m
above the base of an elevator shaft. It is raised to 100 m
above the base of the shaft, where the cable holding it
breaks. The elevator falls freely to the base of the shaft and
strikes a strong spring. The spring is designed to bring the
elevator to rest and, by means of a catch arrangement, to
hold the elevator at the position of maximum spring
compression. Assuming the entire process to be frictionless,
and taking g = 9.8m/s2, calculate:
 Problem continue…
 The potential energy of the elevator in its initial position
relative to the base of the shaft
 The work done in raising the elevator
 The potential energy of the elevator in its highest position
relative to the base of the shaft
 The velocity and kinetic energy of the elevator just before it
strikes the spring
 The potential energy of the compressed spring
 The energy of the system consisting of the elevator and spring
at the start of the process, when the elevator reaches its
maximum height, just before the elevator strikes the spring,
and after the elevator has come to rest
 Problem
Consider the cylinder filled with air and with the piston and
spring arrangement shown in the figure. The external atmospheric
pressure is 1 bar, the initial temperature of the air is 25°C, the no-
load length of the spring is 50 cm, the spring constant is 40 000
N/m, the frictionless piston weighs 500 kg, and the constant-
volume heat capacity of air can be taken to be constant at 20.3
J/(mol K). Assume air is an ideal gas. Compute

a. The initial pressure of the gas in the cylinder

b. How much heat must be added to the gas in the cylinder for the
spring to compress 2 cm
Problem Schematic
 Class Objectives
 Understand Potential and Kinetic Energy

 Understand the concept of Internal Energy

 Understand the difference between Heat and Work

 Understand the Conventions and Terminology used in energy

balance

 Understand and apply the first Law of Thermodynamics to closed

systems

 Understand the difference between state and non-state functions

 Understand the difference between Chemical and mechanical

Equilibrium

 Apply Phase rule at Equilibrium

 STATE FUNCTION
 PV=nRT

 For a given value of V & P, T is determined by the ideal

gas law (For IDEAL GASSES)

 No matter what the changes takes place but by fixing the

P & V, T is fixed.

 Such properties which do not depend on the past history

of the system are termed as STATE FUNCTIONS

 Internal energy is a state function

 STATE Functions
 For state function differential is change in its
infinitesimal value
P2 V2

ò dP = DP ò dV = DV
P1 V1

 However for heat and work differential is an

infinitesimal amount and are non state functions
Q W

ò dQ = Q ò dW = W
0 0
 Problem
When a system is taken from state ‘a’ to
state ‘b’ in figure along path acb, 100 J of
heat flows into the system and the system
does 40 J of work.
1. How much heat flows into the system
along path aeb if the work done by the
system is 20 J?
2. The system returns from b to a along
path bda. If the work done on the
system is 30 J, does the system absorb
or liberate heat? How much?
 Class Objectives
 Understand Potential and Kinetic Energy

 Understand the concept of Internal Energy

 Understand the difference between Heat and Work

 Understand the Conventions and Terminology used in energy

balance

 Understand and apply the first Law of Thermodynamics to closed

systems

 Understand the difference between state and non-state functions

 Understand the difference between Chemical and mechanical

Equilibrium

 Apply Phase rule at Equilibrium

 Equilibrium

 Mechanical Equilibrium; Thermal Equilibrium;

Chemical Equilibrium

 N2 + 3H2 2NH3
 Class Objectives
 Understand Potential and Kinetic Energy

 Understand the concept of Internal Energy

 Understand the difference between Heat and Work

 Understand the Conventions and Terminology used in energy

balance

 Understand and apply the first Law of Thermodynamics to closed

systems

 Understand the difference between state and non-state functions

 Understand the difference between Chemical and mechanical

Equilibrium

 Apply Phase rule at Equilibrium

 Phase rule
 For a pure gas; If P & V is defined then all of its state
properties may be calculated and are fixed.
 So the degree of freedom for a pure gas is ‘2’
 For a liquid in equilibrium to its vapor, if only
temperature is provided all other properties will be fixed
 OR
 For a liquid in equilibrium to its vapor, if only pressure is
provided all other properties will be fixed
 Degree of freedom for such system is ‘1’
 Phase Rule
 F=2–π+N
 Where
 F = degree of freedom
 π = Number of phases in equilibrium
 N = Number of components

 PHASE RULE ONLY APPLY ON THE EQUILIBRIUM

CONDITIONS
 Problem
How many degrees of freedom has each of the following
systems?

1. Liquid water in equilibrium with its vapor

2. Liquid water in equilibrium with a mixture of water

vapor and nitrogen

3. A liquid solution of alcohol in water in equilibrium with

its vapor
 Class Objectives
 Understand Potential and Kinetic Energy

 Understand the concept of Internal Energy

 Understand the difference between Heat and Work

 Understand the Conventions and Terminology used in energy

balance

 Understand and apply the first Law of Thermodynamics to closed

systems

 Understand the difference between state and non-state functions

 Understand the difference between Chemical and mechanical

Equilibrium

 Apply Phase rule at Equilibrium