Chemical Engineering

Thermodynamics I
CME 220

Dr. Kathleen Haigh

Assistant Professor
 Chapter 2 – Part 2

The First Law and Other

Basic Concepts
 A brief review of heat capacity

Mass Balance of an Open System

Outline Energy Balance of an Open System

Energy Balance for Steady State

Systematic approach to problem

solving
Some comments on Specific Heats
 Specific Heats

Definition:

The amount of energy required to raise the temperature

of a unit mass of a substance by one degree.
5 kJ

m  1 kg
T  1o C
Specific heat  5 kJ / kg.o C

5
Internal Energy & Enthalpy Formulation Using Specific
Heats

 u   h 
Cv    Cp   
 T  v  T  p
Cv & Cp are properties

J/kg.K OR Btu/lbm.R

Constant volume Constant

process pressure process

6
Internal Energy & Enthalpy Formulation Using Specific
Heats

• Cv and Cp are obtained in the lab under constant

volume and constant pressure conditions – can
still be used in calculations any other process
regardless of pressure and volume
• Cv is always less than Cp
– Similar for liquid and solids

7
 Specific Heat of Ideal Gases

For ideal gases the specific internal energy is a

function of temperature.
We can show that for ideal gases also specific
enthalpy is a function of just the temperature.
See below:

H = U + PV = U + RT dH = dU + RdT

dH = Cp dT dU = Cv dT

Cp = Cv + R (kJ/kg.K)

Cp = Cv + Ru (kJ/kmol.K)

8
Mass and Energy Balances for Open
Systems
Measures of Flow

There are four common measures of flow:

Specific density

Mass flowrate m
  Mn
m
Molar flowrate n   uA
m

Volumetric flowrate q n  uA

q  uA
Velocity u
molar density
 Mass balance for open systems 1/2
The region of space identified for analysis of
open systems is called a control volume.

The simple mass balance equation is: :

Input rate + Generation rate =

Output rate + Accumulation rate
With no reaction, rate of generation is zero, then:

Accumulation rate + Output rate - Input rate = 0

dm cv
Accumulation rate =
dt
Input rate = m1  m2

Output rate = m 3
dm cv
So,  m 3  m 1  m 2  0
dt
 Mass balance for open systems 2/2
dm cv dm cv “cv” for control volume
 m 3  m 1  m 2  0  m fs  0
dt dt “fs” for flowing streams

dm cv
When:   uA
m  uA fs  0
dt
At steady state:
dm cv
0 uA fs  0
dt
When there is a single entrance and a single exit stream, the mass flowrate is the
same for both streams:

1u1 A1  2u2 A2  0 Or,   const  1u1 A1  2u2 A2

m

u1 A1 u2 A2 uA
Because specific volume is the reciprocal of density: m   
V1 V2 V
General energy balance for open systems 1/2
Energy like mass is conserved.
Each unit mass of stream carries with it a total
energy in its internal, kinetic and potential form:

 1 
E  U  u 2  zg m
 2 
The overall energy balances gives:

d (mU ) cv  1 2   Q Heat transfer rate

  U  u  zg m   Q  Wtotal
dt  2   fs Wtotal
Work transfer rate

The total rate work can include different forms. We can separate the work due to
moving the flowing streams through entrances and exits (W’) from other forms of
work (W) associated with expansion, contraction or stirring :
General energy balance for open systems 2/2
The preceding equation may be written:

  
  U  u 2  zg m   Q  PV m  fs  W
d (mU ) cv 1
dt  2   fs

Combination of terms in accord with : H ≡ U + PV

d (mU ) cv  1 2  
   H  u  zg m   Q  W
dt  2   fs
For many applications, kinetic and potential energy changes in the flowing
streams are negligible which simplifies the equation to:

 Hm  fs  Q  W
d (mU ) cv
dt
 Energy balances for steady state flow
processes 1/2
d (mU ) cv No expansion of the control volume is possible and
At steady state: 0 the only work of the process is shaft work (Ws)
dt

 1  
So:   H  u 2  zg m   Q  W s
 2   fs

When the control volume has one  1 2  Q W s

entrance and one exit. The same mass  H  u  zg     Q  Ws
 2  m m
 
flowrate applies to both streams:
This equation is the mathematical
u 2

expression of the first law for a steady
H   gz  Q  Ws state, steady-flow process between one
2
entrance and one exit (in SI system)
u 2 g
H   z  Q  Ws (English system)
2gc gc
 Energy balances for steady state flow
processes 2/2

In many applications, kinetic and potential energy

terms are negligible compared with other terms. H  Q  Ws
This reduces the previous equation to:

This expression of the first law for a steady state,

steady flow process is analogous to the equation U  Q  W
of a non flow process:

So, Enthalpy is the thermodynamic property of importance for an open

system while internal energy is the thermodynamic property of
importance for a closed system
A systematic approach to problem solving

Step1: Draw a sketch and identify the system. System

V 1 / V2
Step2: List the given information in the sketch. T1 / T2
P 1 / P2

Step3: Check for special processes. Isotherm / Isobar / Adiabatic

Quasi equilibrium (Ek = Ep = 0)

Step4: State any assumptions. Ideal gas assumption

Conservation of mass
Step5: Apply the conservation equation. Conservation of energy

P
Step6: Draw a process diagram.
V

Step7: Determine the required properties and unknowns.

What is shaft work?

Shaft work is the work that is put into or extracted from a rotating turbo-
machine component. It is one of several ways that work can cross a system
boundary.

Components such as turbines, pumps, and compressors all operate by

transferring energy to or from the working fluid through a series of blades
rotating on a shaft.

Probably the simplest type of shaft work is the rotational motion generated
by windmills. The energy from the rotating shaft is converted into electricity
and hence can produce work.