Chemical Engineering

Thermodynamics – I
ChE–214
Aqeel Ahmad TAIMOOR
 Class Objectives
 Understand the concept of Enthalpy and why it is different
from internal energy
 Understand how the enthalpy is determined experimentally
 Understand the concept of heat capacity and difference
between constant volume and constant pressure heat
capacities
 Understand the terminology for open systems
 Apply the first law of thermodynamics to open system (steady
& unsteady state)
 Understand the phase diagrams of Pure Species
 Understand steam tables and how are they related to phase
diagram of water
 Class Objectives
 Understand the concept of Enthalpy and why it is different
from internal energy
 Understand how the enthalpy is determined experimentally
 Understand the concept of heat capacity and difference
between constant volume and constant pressure heat
capacities
 Understand the terminology for open systems
 Apply the first law of thermodynamics to open system (steady
& unsteady state)
 Understand the phase diagrams of Pure Species
 Understand steam tables and how are they related to phase
diagram of water
 Enthalpy

 Energy content of a stationary

system is internal energy

 What if the system starts to

move or flow?

 Temperature energy change

 Pressure energy change

 Volume energy change

 Enthalpy
 Energy change in flow
process = dU + d(PV)

 This is called enthalpy

defined as

 Total energy content of

molecules under shear
stress!
 Probelm
 Calculate ΔU and ΔH for 1 kg of water when it is
vaporized at the constant temperature of 100 oC and the
constant pressure of 101.325 kPa. The specific volumes
of liquid and vapor water at these conditions are 0.00104
and 1.673 m3/kg. For this change, heat in the amount of
2256.9 kJ is added to the water.
 Class Objectives
 Understand the concept of Enthalpy and why it is different
from internal energy
 Understand how the enthalpy is determined experimentally
 Understand the concept of heat capacity and difference
between constant volume and constant pressure heat
capacities
 Understand the terminology for open systems
 Apply the first law of thermodynamics to open system (steady
& unsteady state)
 Understand the phase diagrams of Pure Species
 Understand steam tables and how are they related to phase
diagram of water
 Flow Calorimeter
 Flow calorimeter is a device to measure enthalpy

 Measure of enthalpy is beneficial as it is a state function

 Problem
For the flow calorimeter just discussed, the following data
are taken with water as the test fluid:

Flow rate = 4.15 g/s; T1 = 0 oC; T2 = 300 oC; P2 = 3 bar

Rate of heat addition from resistance heater = 12740W

The water is completely vaporized in the process. Calculate

the enthalpy of steam at 300 oC and 3 bar based on H = 0
for liquid water at 0 oC.
 Class Objectives
 Understand the concept of Enthalpy and why it is different
from internal energy
 Understand how the enthalpy is determined experimentally
 Understand the concept of heat capacity and difference
between constant volume and constant pressure heat
capacities
 Understand the terminology for open systems
 Apply the first law of thermodynamics to open system (steady
& unsteady state)
 Understand the phase diagrams of Pure Species
 Understand steam tables and how are they related to phase
diagram of water
 Heat Capacity
 The old definition

 Amount of energy required to raise the temperature of a

unit mass substance by 1 degree.

 Units = J/mol/K or J/kg/K

 For constant volume processes

 CV = (dU/dT )V
T2
DU = ò CV dT
T1
 Heat Capacity
 For Constant Pressure process

 CP = (dH/dT )P

 dH = CpdT
T2
DH = ò CP dT
T1
 Problem
Air at 1 bar and 25 oC is compressed to 5 bar and 25 oC by two
different mechanically reversible processes:
1. Cooling at constant pressure followed by heating at constant
volume
2. Heating at constant volume followed by cooling at constant
pressure
Calculate the heat and work requirements and ΔU and ΔH of the
air for each path. The following heat capacities for air may be
assumed independent of temperature:
CV = 20.78 J/mol/K; CP = 29.1 J/mol/K
Assume also for air that PV/T is a constant, regardless of the
changes it undergoes. At 25 oC and 1 bar the molar volume of air
is 0.02479 m3/mol.
 Problem
Calculate the internal energy and enthalpy changes that
occur when air is changed from an initial state of 277 K and
10 bar, where its molar volume is 2.28 m3/kmol to a final
state of 333 K and 1 atm. Assume for air that PV/T is
constant and that CV = 21 and CP = 29.3 kJ/kmol/K.
 Class Objectives
 Understand the concept of Enthalpy and why it is different
from internal energy
 Understand how the enthalpy is determined experimentally
 Understand the concept of heat capacity and difference
between constant volume and constant pressure heat
capacities
 Understand the terminology for open systems
 Apply the first law of thermodynamics to open system (steady
& unsteady state)
 Understand the phase diagrams of Pure Species
 Understand steam tables and how are they related to phase
diagram of water
 Open system balance
 For open system flow rates will be used

 Mass flow rate m

 Molar flow rate n

 Volumetric flow rate q

 Other relations

m = Mn q = uA
m = uAr n = uAr̂
 Example
 Liquid n-hexane flows at a rate of 0.75kg/s in a pipe
with inside diameter D = 5cm. What are volumetric and
molar flow rates? Also calculate the velocity of the n-
hexane. Calculate these quantities when the diameter is
reduced to 2cm for constant mass flow rate. Assume
liquid n-hexane density = 659kg/m3
 Class Objectives
 Understand the concept of Enthalpy and why it is different
from internal energy
 Understand how the enthalpy is determined experimentally
 Understand the concept of heat capacity and difference
between constant volume and constant pressure heat
capacities
 Understand the terminology for open systems
 Apply the first law of thermodynamics to open system (steady
& unsteady state)
 Understand the phase diagrams of Pure Species
 Understand steam tables and how are they related to phase
diagram of water
 Mass balance for open
system
 In = out + Accumulation
dmcv
m1 + m2 = m3 +
dt
dmcv
+ D(m) = 0
dt
dmcv
+ D(ruA) = 0
dt
 For steady state

r1u1A1 = r2u2 A2 (Continuity - Equation)

 Energy Balance for the
open system

 In = out + Accumulation

d(mU)cv
+ D éë(H + 1 u2 + zg)mùû = Q +W
dt 2
 Energy Balance for the
open system
d(mU)cv
+ D éë(H + 1 u2 + zg)mùû = Q +W
dt 2
 For steady state processes

D éë(H + 1 u2 + zg)mùû = Q +W
2
 Bernoulli’s Equation
 If kinetic and potential energy difference is negligible then

DH = Q +W
 Problem

A storage tank is being used in a chemical plant to dampen

fluctuations in the flow to a downstream chemical reactor.
The exit flow from this tank will be kept constant at 1.5
kg/s; if the instantaneous flow into the tank exceeds this, the
level in the tank will rise, while if the instantaneous flow is
less, the level in the tank will drop. If the instantaneous flow
into the storage tank is 1.2 kg/s, what is the rate of change
of mass in the tank?
 Problem
Gas is being removed from a high-pressure storage tank
through a device that removes 1 percent of the current
contents of the tank each minute. If the tank initially
contains 1000 mols of gas, how much will remain at the end
of 20 minutes?
 Problem
An open cylindrical tank with a base area of 1 m2 and a height of
10 m contains 5 m3 of water. As a result of corrosion, the tank
develops a leak at its bottom. The rate at which water leaves the
tank through the leak is:

Leak Rate (m 3 /s)  0.5 P

where ΔP is the pressure difference in bar between the fluid at the
base of the tank and the atmosphere. (You will learn about the
origin of this equation in a course dealing with fluid flow.)

Determine the amount of water in the tank at any time.

 Problem
A compressed-air tank is to be repressurized to 40 bar by
being connected to a high-pressure line containing air at 50
bar and 20°C. The repressurization of the tank occurs so
quickly that the process can be assumed to be adiabatic;
also, there is no heat transfer from the air to the tank. For
this illustration, assume air to be an ideal gas with

a. If the tank initially contains air at 1 bar and 20°C, what

will be the temperature of the air in the tank at the end
of the filling process?

b. After a sufficiently long period of time, the gas in the

tank is found to be at room temperature (20°C) because
of heat exchange with the tank and the atmosphere.
What is the new pressure of air in the tank?

c. How much heat is transferred from or in to the tank?

 Problem
 An insulated electrically heated tank for hot water
contains 190 kg of liquid water at 60 oC when a power
outage occurs. If water is withdrawn from the tank at a
steady state of m = 0.2 kg/s, how long will it take for the
temperature of the water in the tank to drop from 60 to
35 oC? Assume cold water enters the tank at 10 oC, and
negligible heat losses from the tank. For liquid water let
CV = CP = C, independent of T and P.
 Problem
Air at 1 bar and 25 oC enters a compressor at low velocity,
discharges at 3 bar, and enters a nozzle in which it expands
to a final velocity of 600 m/s at the initial conditions of
pressure and temperature. If the work of compression is 240
kJ per kg of air, how much heat must be removed during
compression?
 Problem
Water at 93.5 oC is pumped from a storage tank at the rate
of 3.15 x 10-3 m3/s. The motor for the pump supplies work
at the rate of 1.5 kW. The water goes through a heat
exchanger, giving up heat at the rate of 700 kW, and is
delivered to a second storage tank at an elevation 15 m
above the first tank. What is the temperature of the water
delivered to the second tank?
 Problem
Water in a lake initially contains a pollutant at a parts-per-million
concentration. This pollutant is no longer present in the water entering the
lake. The rate of inflow of water to the lake from a creek is constant and
equal to the rate of outflow, so the lake volume does not change.

a. Assuming the water in the lake is well mixed, so its composition is

uniform and the pollutant concentration in the exit stream is the same
as in the lake, estimate the number of lake volumes of water that must
be added to the lake and then leave in order for the concentration of the
pollutant in the water to decrease to one-half of its initial concentration.

b. How many lake volumes would it take for the concentration of the
pollutant in the lake to decrease to one-tenth of its initial concentration?

c. If the volume of water in the lake is equal to the inflow for a one-year
period, assuming the inflow of water is uniform in time, how long
would it take for the concentration of the pollutant in the lake to
decrease to one-half and one-tenth of its initial concentration?
 Class Objectives
 Understand the concept of Enthalpy and why it is different
from internal energy
 Understand how the enthalpy is determined experimentally
 Understand the concept of heat capacity and difference
between constant volume and constant pressure heat
capacities
 Understand the terminology for open systems
 Apply the first law of thermodynamics to open system (steady
& unsteady state)
 Understand the phase diagrams of Pure Species
 Understand steam tables and how are they related to phase
diagram of water
 Volumetric Properties of
fluid
 Volume of fluid is required to design various chemical
equipment

 Volume is a function of temperature & pressure

 The least complex equation representing the relation

between P, V & T is the ideal gas Law

 PV=RT

 Such equations relating P, V & T are termed as equations

of state
Pure Component Diagram

Fusion Curve

Vaporization Curve

Sublimation Curve
P-T Diagram (Pure Substance)
P-V Diagram (Pure Substance)
 Class Objectives
 Understand the concept of Enthalpy and why it is different
from internal energy
 Understand how the enthalpy is determined experimentally
 Understand the concept of heat capacity and difference
between constant volume and constant pressure heat
capacities
 Understand the terminology for open systems
 Apply the first law of thermodynamics to open system (steady
& unsteady state)
 Understand the phase diagrams of Pure Species
 Understand steam tables and how are they related to phase
diagram of water
Steam Tables
Steam Tables
 Problem
For the data in steam tables, find the

1. Specific volume of superheated steam at 816 kPa and

512 oC

2. Temperature and specific entropy of superheated steam

at P = 2950 kPa and H = 3150.6 kJ/kg
 Class Objectives
 Understand the concept of Enthalpy and why it is different
from internal energy
 Understand how the enthalpy is determined experimentally
 Understand the concept of heat capacity and difference
between constant volume and constant pressure heat
capacities
 Understand the terminology for open systems
 Apply the first law of thermodynamics to open system (steady
& unsteady state)
 Understand the phase diagrams of Pure Species
 Understand steam tables and how are they related to phase
diagram of water