TKM-307

Termodinamika Teknik Kimia I

Basic Principles & First Law

The Scope of Thermodynamics

Thermodynamics deals with transformations of energy of all ki
nds from one form to another.
The general restrictions within which all such transformations
are observed to occur are known as the first and second la
w of thermodynamics. These laws cannot be proved in the
mathematical sense. Rather, their validity rests upon experi
ence.
The universal applicability of thermodynamics is shown by the
fact that it is employed alike by physicists, chemists, and en
gineer. The basic principles are always the same, but the ap
plications differ.

Chemical Engineering Thermodynamic

s
The chemical engineer must be able to cope a wide variety of
problems viz. the determination of heat & work requirement
s for physical & chemical processes & the determination of
equilibrium conditions for chemical reactions and for the tra
nsfer of chemical species between phases.
Thermodynamic consideration alone are not sufficient to allo
w calculation of the rates of chemical or physical processes
, because rates depend on both driving force & resistance.
Driving forces are thermodynamic variables, resistances ar
e not.

Chemical Engineering Thermodynamic

s
Thermodynamics is a macroscopic-property formulation. It ca
nnot reveal the microscopic (molecular) mechanisms of ph
ysical or chemical processes. But, on the other hand, know
ledge of the microscopic behavior of matter can be useful i
n the calculation of the thermodynamic properties.
Such property values are essential to the practical application
of thermodynamics; numerical results of thermodynamic ar
e accurate only to the extent that the required data are acc
urate.
The chemical engineer must deal with many chemical specie
s & their mixtures, and experimental data are often unavail
able.

Applying Thermodynamics

The application of thermodynamics to any real probl

em starts with the identification of a particular body o
f matters as the focus of attention. This quantity of m
atter is called the system, and its thermodynamic sta
te is defined by a few measureable macroscopic pro
perties:
Force
Temperature
Volume: specific volume, molar volume, density
Pressure: gauge pressure, absolute pressure

Pressure
The reading on a mercury manometer at 70 oF (open
to the atmosphere at one end) is 25,62 in. The loc
al acceleration of gravity is 32,243 ft/s 2. Atmospher
ic pressure is 19,86 inHg. What is the absolute pre
ssure in (psia) being measured? The density of m
ercury at 70 oF is 13,543 g/cm3.

Unit Conversion
Convert of physical parameters below:
500 oF = .. K = .. oC = .. R
R = 8,314 J/mol.K = .. Btu/lbmol.R = .. cmHg.cm
3
/mol.K = .. kPa.m3/mol.K
4500 kW = .. Btu/jam = ..lbf.ft/detik = .. kgf.m/
detik

Thermodynamics Variable: Work, Energy & Heat

Work W is done whenever a force acts through a distance. Th
e quantity of work done is defined by the equation:
F is the component of the force acting in the direction of the dis
placement dl.

dW F dl

In engineering thermodynamics an important type of work is th

at which accompanies a change of volume of a fluid, i.e. com
pression or expansion.
V2

W P dV
V1

2
A gas is confined in a 0.47-m-diameter cylinder by piston, on
which rest a weight. The mass of the piston and weight tog
ether is 150 kg. The local acceleration of gravity is 9.813 m
s-2, and atmospheric pressure is 101.57 kPa.
a. What is the force in newton exerted on the gas by atmosp
here, the piston and the weight, assuming no friction betw
een the piston and cylinder
b. What is the pressure of the gas in kPa
c. If the gas in the cylinder is heated, it expands, pushing the
piston & weight upward. If the piston & weight are raised 1
5 cm, what is the work done by the gas in kJ
d. What is the change in potential energy in kJ of the piston
& weight?

Work & Energy

Work done on a body in accelerating it from an initial velocity
u1 to a final velocity of u2 is equal to the change of kinetic e
nergy of the body mu2/2
Work done on a body in raising it through the distance z2-z1 is
equal to the change in the quantity of potential energy mgz
If the work done on a body in accelerating it or in elevating it
can subsequently be recovered, then the body by virtue of
its velocity or elevation must contain the ability or capacity
to do this work.
Energy is the capacity of a body for doing work

Work
An automobile having a mass of 1,250 kg is travelin
g at 40 m s-1. What is its kinetic energy in kJ? How
much work must be done to bring it to a stop?
Liquid water at 0oC and atmospheric pressure has a
density of 1.000 g/cm3. At this condition, ice has a
density of 0.917g/cm3.How much work is done at t
hese conditions by 1 kg of ice as it melts to liquid
water?

Work: Energy in Transit

When work is done, it is done by the surroundings on the syst
em, or vice versa, and energy is transferred from the surro
undings to the system, or vice versa. It is only during this tr
ansfer that the form of energy known as work exist.
In contrast, kinetic & potential energy reside with the system.
Their value, however, are measured with reference to the
surroundings, i.e. kinetic energy depends on velocity with r
espect to the surroundings, and potential energy depends
on eleveation with respect to a datum level.
Change in kinetic and potential energy do not depend on thes
e reference conditions, provided they are fixed.

Heat & Energy

Heat is another form of energy that always flows from a highe
r temperature to a lower temperature. The rate of heat tran
sfer is proportional to the temperature difference between t
he two bodies.
In the thermodynamic sense, heat is never regard as being st
ored within a body. Like work, it exist only as energy in tran
sit between a system and its surroundings.
When energy in the form of heat is added to a body, it is store
d as kinetic & potential energy of the atoms and molecules
making up the body.

Internal Energy U
Kinetic & potential energy are energy which the substance m
ay posses as a result of its macroscopic position or motion.
They can be regarded as external form of energy because
their numerical values refer to the surroundings.
In contrast, internal energy of a substance refers to the energ
y of the molecule making up the substance. Although absol
ute values of internal energy are unknown, this is not a dis
advantage in thermodynamic analysis, because only chan
ges in internal energy is required.

First Law of Thermodynamics

Although energy assumes many forms, the total quantity of e
nergy is constant, and when energy disappears in one for
m it appears simultaneously in other forms.
The first law applies to the system and surroundings, NOT to
the system alone. For closed system when only heat and/o
r work is transferred:

energy of surroundings Q W

energy of system

U E

When no external energy change:

U E Q W

U Q W
dU dQ dW

Thermodynamic State and State Functi

on
State functions are quantities which depend only on present con
ditions, however reached. State functions can be expressed
mathematically as functions of thermodynamic coordinates s
uch as temperature & pressure, their value can always be ide
ntified with points on a graph.
Viz.Nitrogen at 300 K & 1 bar has a definite set properties: sp
ecific volume, a definite viscosity, a definite thermal conductiv
ity, etc.
Internal energy is a state function, and is therefore, a property o
f the system.
Work & heat are not state functions because they depend on pa
th/process. They cannot be identified with points on a graph,
but rather are represented by areas.

Thermodynamic State and State Functi

on
State Functions
Represent a property of a
system and always has a
value P
2

dP P

P1

U2

dU U

Not State Functions

Appear only when changes
are caused in a system by a
process, which requires time
dQ Q

dW W

U1

Work & heat ARE NOT state functions but

the diiference: Q W IS a state function

Example
A gas is confined in a cylinder by a piston. The initialpressure
of the gas is 7 bar, and the volume is 0.1 m 3. The piston is
held in place by latches in the cylinder wall. The whole app
aratus is placed in air at standard atmospheric pressure of
101.33 kPa.
What is the energy change of the apparatus if the retaining la
tches are removed so that the gas suddenly expands to do
uble its initial value? The piston is again held by latches at
the end of the process. Assume the rate of heat exchange
between the apparatus and the surrounding air slow comp
ared with the rate at which the process occur.

Intensive vs Extensive Property

Extensive

Intensive

Depend on the quantity in

volved
Double when the quantity
of material is doubled
V, U,.

Independent of the quanti

ty involved
Fix even though the quatit
y of material changed
P, T

Volume is an extensive property

BUT
specific volume and molar volume are intensive properties

Entalphy H
Entalphy is another thermodynamic function defined as:

H U PV
Since U, P & V are all state functions, H must also be a state fu
nction.

dH dU d(PV )

H U (PV )
Like V & U, H is an extensive property
Specific entalphy, h, is of course, an intensive property

Example
Calculate U and H for 1 kg of water when it is vap
orized at the constant temperature of 100 oC and t
he constant pressure of 101.33 kPa. The specific
volumes of liquid & vapor water at these condition
s are 0.00104 & 1.673 m3/kg. For this change, hea
t in the amount of 2256.9 kJ is added to the water.

Problem 2.1 (1)

An insulated and nonconducting container filled with 10 kg of wa
ter at 20oC is fitted with a stirrer. The stirrer is made to turn by
gravity acting on a weight of mass 25 kg. The weight falls slo
wly through a distance of 10 m in driving the stirrer. Assuming
that all work done on the weight is transferred to the water an
d that the local acceleration of gravity is 9.8 ms-2, determine:
a. The amount of work done on the water
b. The internal-energy change of the water
c. The final temperature of the water
d. The amount of heat that must be removed from water to retur
n it to its initial temperature

Problem 2.1 (2)

An insulated and nonconducting container filled with 10 kg of wa
ter at 20oC is fitted with a stirrer. The stirrer is made to turn by
gravity acting on a weight of mass 25 kg. The weight falls slo
wly through a distance of 10 m in driving the stirrer. Assuming
that all work done on the weight is transferred to the water an
d that the local acceleration of gravity is 9.8 ms-2, determine th
e total energy change if the universe because of:
a. The process of lowering the weight
b. The process of cooling the water back to its initial temperatur
e
c. Both processes together

Problem 2.4
Liquid water at 100oC and 1 bar has an internal en
ergy (on an arbitrary scale) of 419.0 kJ/kg & a spe
cific volume of 1.044 cm3/g.
a.What is its enthalpy?
b. The water is brought to the vapor state at 200 oC
and 800 kPa, where its entalphy is 2838.6 kJ/k
g and its specific volume is 260.79 cm 3/g. Calcul
ate H & U for the process.

First Law Expression for Steady-state Flow Proces

s

E K u 2 u1 12 u 2
1
2

1
2

E P z 2 g z1g gz
W1 P1A1

V1
P1V1
A1

W2 P2 A 2

V2
P2 V2
A2

W Ws W2 W1

u 2
U
gz Q Ws P2 V2 P1V1
2
u 2
H
gz Q Ws
2

When no external energy change:

H Q Ws

Example
Air at 1 bar & 25oC enters a compressor at low veloc
ity, discharges at 3 bar, & enters a nozzle in which
it expands to a final velocity of 600 ms -1 at the initi
al conditions of pressure & temperature. If the wo
rk of compression is 240 kJ/kg of air, how much h
eat must be removed during compression?

Problem 2.10
Liquid water at 70 oF flows in a straight horizontal pipe in whic
h there is no exchange of either work or heat with the surro
undings. Its velocity is 30 ft/s in a pipe with an internal dia
meter of 1 in until it flows into a section where the pipe dia
meter abruptly increases.
a. What is the entalphy change of water if the downstream d
iameter is 1.5 in?
b. What is the entalphy change of water if the downstream d
iameter is 3 in?
c. What is the maximum change in entalphy for an enlargem
ent in the pipe?

Problem 2.11
Water flows through a horizontal coil heated from th
e outside by high-temperature flue gases. As it pa
sses through the coil the water changes state from
2 atm & 180 oF to 1 atm & 250 oF. Its entering velo
city is 10 ft/s & its its exit velocity is 600 ft/s.
Determine the heat transferred through the coil peru
nit mass of water.
Entalphy of the inlet and outlet water streams are:
Inlet: 148 Btu/lbm
Outlet: 1168.8 Btu/lbm

Steam Table &

Unit Conversion

Complete of steam table as

following:
P, kPa

T, oC

x, %

, m3/kg

h, kJ/kg

s, kJ/kg.K

300

70

...

1200

200

800

4000

0.142

1500

6.0689

Example
To operate a generator, the utility unit generates amount mechanic ener
gy by operating a turbine. The turbine uses steam as working fluid.
Assume that turbine works adiabatically and reversibly. Steam enter
s the turbine at 1.2 MPa and 250 oC and leave the turbine at saturat
ed condition with pressure and vapor quality of 300 kPa and 96.92%
, respectively. Electrical power produced by generator is 10 MW at m
echanical efficiency of 80%.
a. Calculate the change of enthalpy and internal energy of steam (i
n kJ/kg)!
b. Calculate the required mass flow rate of steam (in ton/hour)!
c. Determine the steams temperature leave a turbine (in oC)!

Example
Water at 200oF is pumped from a storage tank at the
rate of 50 gpm. The motor for the pump supplies
work at the rate of 2 hp. The water passes through
a heat exchanger where it gives up heat at the rat
e of 40,000 Btu/min, & is delivered to a second sto
rage tank at an elevation 50 ft above the first tank.
What is the temperature of the water delivered to t
he second tank?

Concept of Process Reversibility

A process is reversible when its direction can be rev
ersed at any point by an infinitesimal change in ex
ternal conditions.
The reversible process is ideal in that it can never be
fully realized; it represents a limit to the performan
ce of actual processes. Results for reversible proc
esses in combination with appropriate efficiencies
yield reasonable approximations of the work for ac
tual processes.
Vocabulary: Irreversible process, dissipative process

Irreversible Process
An irreversible process is a process that cannot return both the
system and the surroundings to their original conditions. That
is, the system & the surroundings would not return to their ori
ginal conditions if the process was reversed. For example, a
n automobile engine does not give back the fuel it took to dri
ve up a hill as it coasts back down the hill.
There are many factors that make a process irreversible. Four
of the most common causes of irreversibility are friction, unre
strained expansion of a fluid, heat transfer through a finite te
mperature difference, and mixing of two different substance
s. These factors are present in real, irreversible processes a
nd prevent these processes from being reversible.

Problem 2.17
The internal energy Ut of an amount of gas is given
by the equation:
t
t

U 1.5PV

Where P is in (psia) and Vt is in (ft)3. The gas underg

oes a mechanically reversible process from an initi
al sate at 1500 psia and 500 R. During the proces
sVt is constant and equal to 10 ft3 and P increases
by 50 percent.
Determine the value for Q and Ht in Btu for the proc
ess

Illustration: Calculation of Work

A cylinder with a piston is used to compress carbon
dioxide from 1 to 20 bar. Assuming that the proces
s can be carried out reversibly and isothermally at
300 K, calculate the work required per mole, given
that at 300 K the P-V-T properties of carbon dioxid
e follow the equation P( - b) = RT with b = -0,000
11 m3/mol

Problem 2.19
The path followed by a gas during a particular mechanically re
versible process is described by the equation:
P aV t c
Where a & c are constants. In the initial state, P1 = 60 bar and
Vt1 =0.002 m3. In the final state, P2 = 20 bar and Vt2 = 0.004
m3. During the process, heat in the amount of 5000 J is tran
sferred to the gas. Determine W and Ut for the process.

Constant Volume Process & Constant Pressure Proces

s
2

Constant Volume
2

P dV 0

Q U

Heat capacity:
U
CV

T V
T2

Q U C V dT
T1

U Q PdV
1

Constant Pressure

U Q PV

H U PV
Heat capacity:
H
CP

T P
T2

Q H C P dT
T1

Q H

Heat Capacity
Five moles of nitrogen at 80oC is contained in a rigid vessel. How
much heat must be added to the system to raise its temperature t
o 300oC if the vessel has a negligible heat capacity?
If the mass of the vessel is 100 kg and if its heat capacity is 0.5 J/g o
C, how much heat is required?
Three moles of nitrogen at 230oC is contained in a piston/cylinder ar
rangement. How much heat must be extracted from this system,
which is kept at constant pressure, to cool it to 80 oC if the heat ca
pacity of the piston & cylinder is neglected?
Take CV = 20.8 and CP = 29.1 J/moloC for nitrogen gas.

Heat Capacity
Five moles of nitrogen at 100oF is contained in a rigid vessel. How
much heat must be added to the system to raise its temperature t
o 400oF if the vessel has a negligible heat capacity?
If the mass of the vessel is 250 lbm and has a heat capacity of 0.12
Btu/lbmoF how much heat is required?
Three moles of nitrogen at 450oF is contained in a piston/cylinder ar
rangement. How much heat must be extracted from this system,
which is kept at constant pressure, to cool it to 100 oF if the heat c
apacity of the piston & cylinder is neglected?
Take CV = 5 and CP = 7 Btu/lbmol oF for nitrogen gas.