Company

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 cooked?

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
kondensor
Equilibrium condition all forces in exact balance

heat

Equilibrium (cont.)
A

Vapor
phase

Liquid
phase
t = 0 minute
(in a certain
P, and T)

Liquid
phase

A composition
mixtures,

t = C minutes
(in a certain

B composition
mixtures,

P, and
T)
Condition
:
Macroscopic
Microscopic

no changes,
static
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
A mixture of steam + liquid water in equilibrium
Changing temperature
will also change the
pressure if vapor-liquid
are in equilibrium

Phase Rule (cont.)

Lets check it out in HYSYS

hoose H2O as selected component

Choose material stream

Choose Peng-Robinson as property package

Go to simulation environment

Phase Rule (cont.)

Lets check it out in HYSYS

Set pressure to 101.325 kPa

Set temperature to 100 oC

Take basis molar flow 1 kgmole/h

to composition, then fill H2O mole fraction with 1, then OK

Phase Rule (cont.)

Lets 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 :
Cek campuran
etanol (1)+ air (2)
T (K)
konsentrasi mol
fraction 0-1 dengan
incremen 0.1 (0,0.1,
x1
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
etanol vs
Temperature also
temperature)
increase to more
than 100 oC

Cook water until boiling point in deep blue sea

What happen when you boil water in high pressure area with pressure
more than 1 atm (101.32 kPa)

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 phaserule
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
N
solution
= 2 (two chemical species) are water and salt

F 23 21

So, degree of freedom

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
2 N
When F = 0
The system is invariant
Equation becomes
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
2 N
dissapear

2 1
3 phase

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
F 2: N 2 2 1 1
a)
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 constanttemperature 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 0.003 m 3 . 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

W t P dV k
t

V1t

V1

V1t 0.03 m 3

dV t
V2t
k ln t
t
V
V1

;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 pressureV
oft 7 bar. Thus
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

efficiency

21000
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, closedsystem process, the heat transferred is equal to the internalenergy 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, closedsystem process, the heat transferred is equal to the enthalpy

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
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

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

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

W

Q
m

system

First Law:
E(system) + E(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
2
2

j
i
(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

W f PjV j m j PiVi m i
j

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
2
2

j
i
j
i

Remember:

H U PV

Open System Energy Balance

d mU
1 2
1 2

mi H i ui zi g m j H j u j z j g Q W s
dt
2
2

i
j

input

output

In general:
d mU
0
Steady state:
dt
one inlet and outlet stream:m i m j m
1 2

m H u gz Q W s
2

1 2
H u gz Q Ws
2

Rate of energy
Rate of energy per
unit mass or mole

Thank
you