Thermodynamics

Part 2: Applications

Psychrometry Equilibrium Thermochemistry

Prof. M.N. SABRY

Ch. 1: Special mixture: Air Water vapor

Prof. M.N. SABRY

Psychrometry
Problem considered
A perfect mixture of perfect gases:
Each component : Perfect Gas
A small quantity of matter may change phase
(Gas Liquid ou Gas Solid)

Simplified Model
gaseous phase is homogeneous and composed of 2 perfect gases
vapor is at low pressure
Treated is a perfect gas, even when close to saturation
Liquid and solid phases are void of dissolved gases
Prof. M.N. SABRY

Definitions
Absolute (Specific) Humidity

= m vap / m a

m vap mass of vapour

m a mass of other gases

= (Pvap V / R vap T ) / (Pa V / R a T ) = (vap / a) (Pvap / Pa)

Relative Humidity

= Pvap / Pvap_sat

(For air and water:

= 0.622 Pvap / Pair )
State of vap.
In mixture

T
Pvap_sat (T ) Saturation pressure
At mixture temperature

Max Quantity of vapor when: = 100%

Starting from state 1, we can :
Cool at const P until state 2 ( reaches 100%)
Add vapor at T const. Until state 3 ( reaches 100%)
(beyond points 2 or 3: condensation)

Pvap_sat 3
1

Pvap

Dew
point

T s Diagramme for
Condensable material

( For air and water: = Pair / (0.622 Pvap_sat (T ))

Prof. M.N. SABRY

Adiabatic Saturation
Air entering
<1

Evaporation
of water

Air leaving
=1

f
1st Law

m a ha1 + m v1 hv1 + m w hf2 = m a ha2 + m v2 hvsat2

But

m w = m v2 - m v1
ha1 + 1 (hv1 - hf2) = ha2 + 2 hfg2

T 1 : Temperature of state 1 (dry bulb)

T 2 : Temperature of state 2 (wet bulb)
T wet bulb T dry bulb

Prof. M.N. SABRY

Psychometric Chart
Obtained from: = 1 = Pair / (0.622 Pvap_sat (T ))
h Tot. = Const
wet bulb = Const

=1

Prof. M.N. SABRY

= Const < 1
(obtained by dividing
Ordinates proportionally)

Air conditionning processes

=

(
2-
1)
(
2- 1)
Dew point
2 2
1

Cooling Heating

Humidification

Cooling and Dehumidification

Drying
Prof. M.N. SABRY

Thermodynamics
Ch2 : Thermodynamic Equilibrium
For Single Component
Equilibrium and thermodynamic potentials

Prof. M.N. SABRY

Equilibrium of an Isolated System

Single component

In general for a control mass :

.
.
Since isolated:
Q = m = 0:

TdS/dt = Q + TdSirrev /dt

dSirrev /dt 0

dS/dt = dSirrev /dt 0

At equilibrium: dS/dt = 0

S = max

Consider an isolated system

Composed of 2 sub-systems (a, b )
exchanging Heat & Work

dS = dSa + dSb
= (dUa+PadVa)/Ta + (dUb +Pb dV b )/T b

Sub
System
a

Sub
System
b

An isolated
system

But: dUa = - dUb ; dVa = - dV b

dS = 0 (1/Ta - 1/T b ) dUa + (Pa/Ta - Pb /T b ) dV b =0
At equilibrium:

Ta = T b ; Pa = Pb
Prof. M.N. SABRY

Exchange of:
- Heat
- Work

Equilibrium depends on constraints

Systm B

System A

(exchange only work)

(exchanging only heat )

Ambient
P = 2 M Pa
T = 300 K

Tamb = 300 K
Pamb = 0.1 M Pa
T = 500 K
P = 0.1 M Pa

Both systems are in equilibrium with ambient,

But final equilibrium depends on constraints

Prof. M.N. SABRY

10

Thermodynamic Potentials
Entropie variation has allowed the study of equilibrium of an isolated system :

T dS = dU + PdV

Gibbs Formula

(isolated: dU total = 0; dV total = 0 dS = 0 at equilibrium)

For other constraints, we need other potentials

dU = T dS PdV
dH = dU + d (VP)
dH = TdS + VdP
Define:
Gibbs Free Energy :

G = H TS
dG = -SdT + VdP

Helmholtz Free Energy :

A = U TS
dA = -SdT PdV
Prof. M.N. SABRY

11

Variation of potentials
For a control masse at P, T constant :
.

TdS/dt = Q + TdSirrev /dt

T const.
d (TS)/dt

P const.

U = min. (if S,V const.)

Also,
at equilibrium: H = min. (if S,P const.)

dH/dt

dG/dt = TdSirrev /dt 0

At equilibrium : dG/dt = 0
G = min. (if P,T const.)
Also, if V, T const. :
.

Properties P
Related to work

Properties
Related to Heat T

Q TdS/dt = dA/dt = TdSirrev /dt 0

At equilibrium : dA/dt = 0
A = min. (if V,T const.)
Prof. M.N. SABRY

To be used if
T, V const.

To be used if
T, P const.

etc.
12

Phase Equilibrium (single component)

Let us study the transition : Liquid vapor at P = const. T = const.
During the transition : Uvap Uliq = Q + W
If transition in equilibrium :

W = P (V vap V liq )

Q=T (Svap Sliq )

Uvap Uliq = T (Svap Sliq ) P(V vap V liq )

G vap = G liq

Another approch (standard) for the study of equilibrium:

Molecules will cross the interface in both directions.
At equilibrium: same number crosses in each direction.
Equilibrium at T & P const. implies:

dG mix = 0
But

dG mix = G liq dm liq + G vap dm vap

dm liq = - dm vap
Prof. M.N. SABRY

0 = (G liq G vap ) dm liq

G vap = G liq
13

Clausius-Clapeyron Relation
If the pressure changes by dP , and temperature by dT
to restore equilibrium :

dG vap = dG liq
d (G vap G liq ) = 0 = (V vap V liq ) dP (Svap Sliq ) dT
dP / dT = (Svap Sliq ) / (V vap V liq )
dP / dT = (Hvap Hliq ) / T (V vap V liq )
Variation of P wrt T
along saturation line

Clausius Clapeyron Relation

Latent Heat hfg

Prof. M.N. SABRY

14

Maxwell Relations
Since G, A, H and U are state variables
Hence, dG, dA, dH and dU are total differentials

dG = SdT + VdP
G T

= S

G P T = V

S P T = V T

Maxw1

dA = SdT PdV

dH = TdS + VdP

dU = T dS PdV

A T V = S

H S P = T

U S V = T

A V T = P

H P S = V

U V S = P

S V

= P T V

Maxw2

T P S = V S P

Maxw3

T V

= P S V

Maxw4

Maxwell Relations
Starting from
mesurable properties (P,V,T )

Prof. M.N. SABRY

Get Non - mesurable

properties (S,H,G )

15

Enthalpy of a real gas

We can easily measure:

h* (T ) = h|P0(T ) By calorimetry :
v=V/m = f(P,T )
.
m h*(T 1)

v=

.
Q

h (P,T )= ?
.
m h*(T 2)
h* (T )=

To get h(P,T ) :

h* =

T

h (P,T )= [h(P,T ) h*(T )] + h*(T)

P

0 h P T dP
But, the potentiel h :

dh = dH/m = Tds + v dP

Gibbs Formula

h P T = T s P T + v

But (Maxw1) : s P T = v T

P
P

h (P, T ) = h * (T ) + v T v T
0

)dP

=0 for an ideal gas

Prof. M.N. SABRY

16

Entropy of a real gas

Gibbs Formula

v,h=

To get entropy s* @ P 0:

s (P,T )= ?

Tds = dh v dP
s* =

dh * (T )
T

s* (T )=

To get s(P,T ) :

h* =

s* =

T

s (P,T )= [s(P,T ) s*(T )] + s*(T)

P

0 s P T dP
But (Maxw1) : s P T = v T

P
P

s (P, T ) = s * (T ) v T P dP
0

N.B.: knowing v, h and s as a function of P and T we can get :

u = h Pv =

g = h Ts =

Prof. M.N. SABRY

a = u Ts =

17

Constructing thermodynamic tables

Starting from:
v = f(P,T )
For each phase

h* (T ) = h|P=c(T )

P = f(T ) For each phase transition

We can calculate for each phase:
P

h (P, T ) = h * (T ) + v T v T
c

u = h Pv =

)dP

s* =

Tref

g = h Ts =

dh * (T )
T

s (P, T ) = s * (T ) v T P dP
c

a = u Ts =

We can calculate for each phase transition:

h = T v dP / dT
s = h / T

Clausius Clapeyron Relation

u =
h P
v

g =
h T
s =0

Prof. M.N. SABRY

a = P
v
18

Thermodynamics
Ch. 3: Thermochemistry

Prof. M.N. SABRY

19

Thermochemistry
Apply to all chemical reactions,
Concentrate on combustion
7% 7%1%

Sources of energy :

38%

24%
23%

Petrol
Gaz Naturel
Charbon
Hydraulique
Nucleaire
Nouvelle

Combustion of
fossil fuel: 85%

Types of fuel:
 Solid

Essentially coal C, rural & urban wastes

 Liquid

Essentially petrol, mixtures of hydrocarbons CnHm (octane=C8H18)

 Gaseous Essentially natural gas, methane CH4 , hydrogen H2

biomass

Prof. M.N. SABRY

Water electrolysis

20

Stoichiometric Mixture
If air quantity is just sufficient for COMPLETE combustion
Stoichiometric mixture
Reactants
CnHm + a O2 + b N2
air

N.B.

Products
c CO2 + d H2O + b N2

Composition by volume: 79% N2, 21% O2

 We neglect rare gases in air (Argon 1%, )

 We neglect formation of nitrogen oxides (except at very high temperature)
 Nitrogen exists because it is heated
 Rich mixture: air < stoichiometric: incomplete combustion but fast, high T
 Poor mixture: air > stoichiometric: complete combustion, T moderate

Prof. M.N. SABRY

21

Mass balance
If stoichiometric:
Reactants
CnHm + a O2 + b N2

Products
c CO2 + d H2O + b N2

air

Equality of C atoms: n = c
Equality of H atoms: m = d/2
Equality of O atoms: 2a = 2c + d
Composition of air: b = 79/21 a = 3.76 a

Example :
C8H18 + 12.5 O2 + 12.5*3.76 N2
8 CO2 + 9 H2O + 12.5*3.76 N2

Mass of fuel: 8*12 + 18*1 = 114

Mass of air : 12.5 (16*2 + 3.76*14*2)= 1382

(Air to Fuel Ratio AFR):

Mass of air / kg fuel

Soichiometric AFR for C8H18

= 1382 / 114 = 12.123

Prof. M.N. SABRY

22

Heat (enthalpy) of formation

For a chemical reaction :
It is important to fix the reference (i.e. level 0) of u and h.
To define u, h
1 kmol of C
Entering at NPT
1 kmol of O2

1 kmol of CO2
Leaving at NPT

Reaction
C + O2 CO2

NPT:

T = 25 + 273 K
P = 0.1 MPa

Q (produced ) = 393.522 MJ

Rules:

 by convention, enthalpy of an element (C, O2, N2, ) is 0 at TPN

 enthalpy of a chemical compound at NPT is:
Enthalpy (or heat) of formation :

hfo (in J/kmol)

hfo (in J/kg)

Heat received during formation reaction

hfo of CO2 = -393.522 MJ/kmol

hfo of CO2 = -32.794 MJ/kg

Prof. M.N. SABRY

23

Applying 1st Law

d
Q& + W& + m& in (h + KE + PE )in m& in (h + KE + PE )in = [ms (u + KE + PE )s ]
dt

where

m& in hin = iR m& i h 0f ,i + h in ,i h TPN ,i

))

m& out hout = jP m& i h 0f , j + h out , j h TPN , j

Definitions

Reference

))

R = Reactants
P = Products

Delta

Adiabatic Flame Temperature

Temperature of products of adiabatic combustion at P const, reactants at NPT
Higher calorific value
Heat produced if reactants et products at NPT, with liquid H2O in products
Lower calorific value
Heat produced if reactants et products at NPT, with vapor H2O in products
Prof. M.N. SABRY

24

Third Law of thermodynamics

To fix the reference of s
3rd Law:
Entropy of a perfect crystal at T = 0 is 0

Prof. M.N. SABRY

25

Equilibrium Many components

Let us mix reactants A & B and products C & D.
at arbitrary proportions
At equilibrium, the number of moles
present for all components:

chemical reaction is
reversible & stoichiometric

A A + B B C C + D D

nA , nB , nC , nD = ?
The degree of advance of a reaction:

dnA = A d

dnC = C d

dnB = B d

dnD = D d

Stoichiomtric number of moles

dG|T,P = gA dnA + gB dnB + gC dnC + gD dnD = 0

0 = ( A gA B gB + C gC + D gD) d

Prof. M.N. SABRY

26

Chemical Potential
For a system with:
1 componant
Work of changing volume only

2 Degrees of Freedom.
dU = TdS PdV (Gibbs Formula)
i.e. U=f(S,V )

For many componants :

ni: Numbre of moles of componant i

U = U ( S, V, n1 , n2 , )

dU = (U/S|V,ni) dS + (U/V|S,ni) dV + i (U/ni|S,V,nj ) dni

If dni=0
In general
Also:

-P

i: Chemical Potential

dU = TdS PdV + i i dni

dH = d(U+PV) = TdS + VdP + i i dni
dA = d(U-TS) = -SdT - PdV + i i dni
dG = d(H-TS) = -SdT + VdP + i i dni
Prof. M.N. SABRY

i =

U
H
=
ni S ,V ,n
ni S , P,n
j i
j i

A
G
=
ni T ,V ,n
ni T , P,n
j i
j i
27

Chemical Equilibrium
For constant T, ideal gas:

0 = ( A G A B G B + C G C + D G D) d
Put: G 0
0 = ( A gA 0 B gB0 + C gC 0 + D gD0)

d gA |T = dhA - TdsA
d gA |T = RT dln PA

+ R
( A lnaA B lnaB + C lnaC + D lnaD)

gA = gA |Po+ RT ln (aA )

Put: ln K = G 0/RT

For an ideal gas: aA = y A P/P0

C + D A B

yCC y DD P
K= 0
y AA y BB P

Prof. M.N. SABRY

28