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LOGO THERMODYNAMICS 1

The First Law and Other Basic Concepts (part 2)

Department of Chemical Engineering, Semarang State University

Dhoni Hartanto S.T., M.T., M.Sc.
 Equilibrium
Have you ever cook?
 Equilibrium (cont.)

Equilibrium is a word denoting a static condition, the absence of change

In thermodynamics, it means not only the absence of change but also the
absence of any tendency toward on macroscopic scale

Other definition, equilibrium is static condition in which no changes occur

in the macroscopic properties of a system with time.
But, in microscopic properties, the condition is not static

Equilibrium condition  all forces in exact balance

condensor

heat
 Equilibrium (cont.)
A B
Vapor
phase

Liquid
Liquid
phase
phase

t = 0 minute t = C minutes
(in a certain “A” composition mixtures, (in a certain “B” composition mixtures,
P, and T) P, and T)
Condition :
Macroscopic no changes, static
Microscopic changes, not static
 Phase Rule

When two intensive thermodynamic properties are set at definite values, the
state of a pure homogeneous fluid is fixed.

In contrast, when two phases are in equilibrium, the state of the system is
fixed when only a single property is specified

Changing temperature
will also change the
101.325 pressure if vapor-liquid
kPa 373.15 K
are in equilibrium

A mixture of steam + liquid water in

equilibrium
 Phase Rule (cont.)
Let’s check it out in HYSYS

Go to fluid
packages

Choose H2O as selected component Choose Peng-Robinson as property package

Go to simulation environment
Choose material stream
 Phase Rule (cont.)
Let’s check it out in HYSYS

Set pressure to 101.325 kPa

Set temperature to 100 oC

Take basis molar flow 1 kgmole/h

Go to composition, then fill H2O mole fraction with 1, then OK
 Phase Rule (cont.)
Let’s check it out in HYSYS

With set the temperature and pressure, HYSYS automatically change the vapor phase
to be 1, it means the water in vapor phase
 Phase Rule (cont.)
Cook water until boiling point in mountain

When the water boil

Pressure less than 1

atm (101.32 kPa)
Temperature also
less than 100 oC

What happen when you boil water in high area such as mountain which the pressure is
less than 1 atm (101.32 kPa)
 Phase Rule (cont.)
Tugas HYSYS :
Cook water until boiling point in deep blue sea
Cek campuran tert-
butanol (1)+ air (2)
T (K) konsentrasi mol
fraction 0-1 dengan
x1 incremen 0.1 (0,0.1,
0,2 dst.)
Vapor fraction = 1
Pada P = 1 atm
Bagaimana
When the water boil perubahan
temperatur,
Pressure more than Buat grafiknya
1 atm (101.32 kPa) (mole fraction tert-
butanol vs
Temperature also temperature)
increase to more Bandingkan dengan
than 100 Co
literatur (VLE tert-
What happen when you boil water in high pressure area butanol (1)+ air (2)
with pressure more than 1 atm (101.32 kPa) pada P = 1 atm)
 Phase Rule (cont.)
Degree of freedom of the system

For any system at equilibrium, the number of independent variables that must be
arbitrarily to establish its intensive state is given by the phase-rule
The phase-rule is intensive property

F  2   N

N : number of chemical species

F : degree of freedom
phi : phase

Example :
Various phase can coexist , it must be in equilibrium
Three-phase system at equilibrium is a saturated aqueous solution at its boiling
point with excess salt crystals present.
 = 3 (three phase) are crystalline salt, the saturated aqueous solution
N = 2 (two chemical species) are water and salt

So, degree of freedom F  23 21

 Phase Rule (cont.)
Degree of freedom of the system

The intensive state of a system at equilibrium is established when its

temperature, pressure, and the composition of all phase are fixed

The phase rule gives the number of variables from this set which
must be arbitrarily specified to fix all remaining phase-rule variables

The minimum degree of freeedom for any system is zero

When F = 0
The system is invariant
Equation becomes   2  N

Value of phi is the maximum number of phase which can coexist at equilibrium
for a system containing N chemical species
 Phase Rule (cont.)
Degree of freedom of the system

For example :
The triple point of water where liquid, vapor, and the common from ice exist
together in equilibrium at 273.16 K (0.01oC) and 0.0061 bar

Any change from these condition causes at least one phase to dissapear
  2 N liquid
  2 1
 3 phase
Water at
0.01oC
0.0061 bar
ice vapor
 Phase Rule (cont.)
How many degrees of freedom has each of the following system :
a) Liquid water in equilibrium with its vapor
b) Liquid water in equilibrium with a mixture of water vapor and nitrogen
c) A liquid solution of alcohol in water in equilibrium with its vapor

Answer :
a) F  2    N  2  2  1  1
In fact, temperature or pressure but not both may be specified for a system
of water in equilibrium with its vapor

b) F  2    N  2  2  2  2
The addition of an inert gas to a system of water in equilibrium with its
vapor changes the characteristic of the system. Temperature and pressure
maybe independtly varied

c) F  2    N  2  2  2  2
The phase-rule variables are temperature, pressure, and the phase
composition
Fixing the mole fraction of water in liquid phase automatically fixes the
mole fraction of the alcohol
 The Reversible Process
A process is reversible when its direction can be reversed at any point
by an infinitesimal change in external conditions.
 The Reversible Process (cont.)
When heated, CaCO3 decompossed forms CaO and CO2

When weight is increased, CO2 pressure is increased and CO2 combines with
CaO to form CaCO3 allowing the weight to fall slowly
 The Reversible Process (cont.)
Summary :

A reversible process has the following condition :

1. Is frictionless
2. Is never more than differentially removed from equilibrium
3. Traverses a succession of equilibrium states
4. Is driven by forces whose imbalance is differential in magnitude
5. Can be reversed at any point by a differential change in external conditions
6. When reversed, retraces its forward path, and restores the initial state of
system and surroundings
 The Reversible Process (cont.)
Mechanically reversible

V2t
W    t P dV t
V1

Example :
A horizontal piston/cylinder arrangement is placed in a constant-temperature
bath. The piston slides in the cylinder with negligible friction, and an external
force holds it in place against an initial gas pressure of 14 bar. The initial gas
volume is 0.03 m3 . The external force on the piston is reduced gradually and
the gas expands isothermally as its volume doubles. If the volume of the gas is
related to its pressure so that the product PVt is constant, what is the work
done by the gas in moving the external force?

How much work would be done if the external force were suddenly reduced to
half its initial value instead of being gradually reduced?
 The Reversible Process (cont.)
Solution :
The process is mechanically reversible
If PVt = k , then P=k/Vt

V2t V2t dV t V2t

W    t P dV   k 
t
t
  k ln t
V1 V1t V V1
V1t  0.03 m 3 ;V2t  0.06 m 3
t
k  PV t  P1V1  (14 . 105 )( 0.03)  42000 J
W  42000 ln 2  29112 J

Final pressure :

k 42000
P2  t   700000 Pa  7 bar
V2 0.06
 The Reversible Process (cont.)
Solution :
In the second case, a half of the initial force has been removed
The gas under goes a sudden expansion against a constant force equivalent to
pressure of 7 bar. Thus V
t
is the same as before and the net work
accomplished equals the equivalent external pressure times the volume change.

W  (7 .105 )(0.06  0.03)  21000 J

This second case is irreversible, and compared with reversible one the
efficiency is

21000
efficiency   0.721 or 72.1%
29112
 Constant V and Constant P Process
Energy balance for a homogeneous closed system of n moles :
d (nU )  dQ  dW

Work in mechanically reversible :

dW   Pd (nV )

Combine this two equation, yield :

d (nU )  dQ  Pd (nV )

General first-law equation for

mechanically reversible and closed
system
 Constant V (volume) Process

In constant total volume process, the work is 0, thus the equation will be :

dQ  d (nU )
Q  n U

Thus for a mechanically reversible, constant-volume, closed-system process,

the heat transferred is equal to the internal-energy change of the system.
 Constant P (Pressure) Process
Arrange the equation below to solve dQ :
d (nU )  dQ  Pd (nV )
yield,
dQ  d (nU )  Pd (nV )

For constant pressure

dQ  d (nU )  Pd (nV )  d [n(U  PV )]

Where U + PV is the definition of enthalpy

H  U  PV
The equation become
dQ  d (nH )
Q  n H

Thus for a mechanically reversible, constant-pressure, closed-system process,

the heat transferred is equal to the enthalpy change of the system.
 Enthalpy

Unit of enthalpy (H) : energy per mole or unit mass

Enthalpy is state function due to U, V, and P are state function

Enthalpi is intensive property

dH  dU  d ( PV )
H  U  ( PV )

These equation apply to a unit mass or a mole of substance

 Heat Capacity

Heat has relation with its effect on the object

This is the origin of the idea that a body has capacity

The smaller the temperature change in a body caused by the transfer of a given
quantity of heat, the greater its capacity

dQ
C
dT

In fact, there are 2 kind of heat capacities are in common use for homogeneous
fluids. Both are state function

There are :
1. Heat capacity at constant volume (Cv)
2. Heat capacity at constant pressure (Cp)
 Heat Capacity at constant volume (Cv)
 Q 
CV   
 T V
dU  CV dT
T2
U   CV dT
T1

For mechanically reversible at constant volume process

T2
Q  n U  n  CV dT
T1
 Heat Capacity at constant pressure (Cp)
 H 
CP   
 T P
dH  C P dT
T2
H   C P dT
T1

For mechanically reversible at constant pressure process :

T2
Q  n H  n  C P dT
T1
 Open System Energy Balance

Q W
system
m

First Law:
DE(system) + DE(surrounding) = 0
Per unit mass containing energy:
1 2
U  u  zg
2
Total energy carried out:
 1 2 
m U  u  zg 
 2 
 Open System Energy Balance

Energy in the system can change due to accumulation or loss :

d  mU 
dt
Thus:

d  mU   1 2   1 2   
  m j U j  u j  z j g    mi U i  ui  zi g   Q  W
 
dt j  2  i  2 

(input) (output)
 Open System Energy Balance

Work: caused by fluid pushing in and out or piston (Wf)

and shaft work (Ws)
W  W  W f s

W f   PjV j m j   PiVi m i
j i
input output
d  mU   1   1 
  m j U j  u 2j  z j g    m i U i  ui2  zi g   Q   PjV j m j   PiVi m i  W s
dt j  2  i  2  j i

Remember: H  U  PV
 Open System Energy Balance

d  mU   1   1 
  m i  H i  ui2  zi g    m j  H j  u 2j  z j g   Q  W s
dt i  2  j  2 
input output
In general:
d  mU 
• Steady state: 0
dt
• one inlet and outlet stream:m i  m j  m

 1 2 
m  H  u  gz   Q  W s Rate of energy
 2 
1 2 Rate of energy per
H  u  gz  Q  Ws
2 unit mass or mole
Thank you