Multivector Review and Training Center

THERMODYNAMICS

Thermodynamics – is the science that is concerned with the conversion of work

into heat energy or vice versa.

Temperature – is the degree of hotness or coldness of a body.

Conversion from one scale to another scale:

At 1 atm pressure,

Units Centigrade Fahrenheit Kelvin Rankine Reamur

C C C C C

100 212 373 672 80

B.P. of H2O

A certain temp. C F K R R

F. P. of H2O 0 32 273 492 0

273 460 0 0 219

Absolute Zero

Conversion Formulas:

F C C K F R C R
C
5
F  32 K  C  273 R  F  460 R
4
C
9 5
9 5
F  C  32 C  K  32 F  R  460 C R
5 4

9
Note: 1. TF  TC OR 5C  9F, also TK  TC
5
2. C, F, K, or K & R
3. C, F, K & R

Heat – form of energy transferred from one body to another as a result of

temperature difference.

Sensible Heat – is the heat absorbed or given off by a substance that changes its
temperature.
Q = mcT

MRTC - 69
Multivector Review and Training Center

where: Q – sensible heat

m – mass
c – specific heat
T = T2 – T1 = change in temperature

Heat Units
1. calorie (cal) 1 cal = 4.186 J
2. kilocalorie (kcal) 1kcal = 1,000 cal
3. Joule (J) 1 BTU = 252 cal
4. British Thermal Unit (BTU)

Specific Heat (c) – is the amount of heat needed to change the temperature of a
unit mass of a substance one degree change in the temperature.

For H2O:
BTU cal cal
c1 1 1
lbm  F g  C g  K

For ice:
BTU cal cal
c  0.5  0.5  0.5
lbm  F g  C g  K

For steam:
BTU cal cal
c  0.48  0.48  0.48
lbm  F g  C g  K
OR
BTU cal cal
c  0.5  0.5  0.5
lbm  F g  C g  K

Change of State

Latent Heat – is the heat that does not affect the temperature of the substance but
changes its state.

a. Latent heat of fusion (Lf) – is the amount of heat per unit mass necessary to
change a substance from the solid to the liquid state at its melting point.
Qf
Lf  OR Q f  mL f
m
cal BTU
For ice, L f  80 OR 144
g lb

MRTC - 70
Multivector Review and Training Center

cal 5 BTU
Also, L f in  L f in
g 9 lb

b. Latent Heat of Vaporization (Lv) – is the amount of heat per unit mass
necessary to change a substance from liquid to vapor at its boiling point.
QV
LV  OR Q V  mL V
m
cal BTU
For water, L V  540 OR 972
g lb
cal 5 BTU
Also, L V in  L V in
g 9 lb

c. Specific Latent Heat of Sublimation of a Substance – is the heat per unit

mass necessary to convert it from the solid to the gaseous state at a given
temperature.

Sublimation – a change of state from solid to gaseous without passing the liquid
state.
For example, dry ice

First Law of Thermodynamics

“When work is totally converted into heat the amount of heat generated bears a
constant ratio to the work done. Similarly, if a certain amount of heat is
transformed into mechanical energy bears a constant ratio to the heat which
disappeared”. This is often called Joule’s Law:
W
J
Q
where: W = work done to produce heat or work produced by heat
Q = heat energy
J = mechanical equivalent of heat
J = 4.186 joules per calorie
J = 4.186 x 107 ergs per calorie
J = 778 ft-lbs per BTU

The Ideal Gas Law

a. Boyle’s Law. At constant temperature, the volume of a sample of gas is
inversely proportional to the absolute pressure applied to the gas.

MRTC - 71
Multivector Review and Training Center

1
If T = constant, then V  .
P
C
V OR PV  C
P
P1V1  P2 V2  Pn Vn  C

b. Charle’s Law. At constant pressure, the volume of a sample of gas is directly

proportional to the absolute temperature.
If P = constant, then V  T .
V
V  CT OR C
T
V1 V2 Vn
  C
T1 T2 Tn

c. Gay-Lussac’s Law sometimes called as Amonton’s Law. At constant

volume, the pressure of a sample of gas is directly proportional to the absolute
temperature.
If V = constant, then P  T .
P
P  CT OR C
T
P1 P2 Pn
  C
T1 T2 Tn

d. Combined or Perfect Gas Law

PV  T
PV
PV  CT OR C
T
P1V1 P2 V2 Pn Vn
  C
T1 T2 Tn

e. Ideal Gas Equation

PV  mRT
where: R = gas constant
R
R
M

MRTC - 72
Multivector Review and Training Center

m
PV  RT
M
m
But m  nM OR n 
M
Hence PV  n RT
where: n  number of moles
grams lb m
M  molecular weight ; or
mole mole
R  universal gas cons tan t
ft  lb
R  1545.32
pmole  R
cal
R  1.9858
g mole  K
J
R  8,314
kg mole  K
Note: In Chemistry, PV = nR*T
where: R* = Ideal Gas Constant = Universal Gas Constant
PV 1 atm 22.4 liters 
R* 
nT 1 mole 273 K 
liter  atm
R *  0.08205
mole  K

Processes of Ideal Gases

Isometric Process – is an internally reversible process of substance in which the

volume remains constant.
T
P
(V, P2) 2
2 T2

1 T1

Q
1
(V, P1) S
V S1
S2

MRTC - 73
Multivector Review and Training Center

Formulas:

1. Gay-Lussac’s Law
P1V1 P2 V2 P1 P2
 OR 
T1 T2 T1 T2
where: V1 = V2

2. WNF = PdV = 0

3. Q = U = U2 – U1
Proof: By Law of Conservation of Energy
Q = P + K + U + WF + WNF
Q = U

4. Change in internal energy (U)

U = U2 – U1 = mcv (T2 – T1)

5. Change in enthalpy (H)

H = H2 – H1 = mcp (T2 – T1)

6. Change in entropy (S)

T2 P
S  S 2  S1  mc v ln  mc v ln 2
T1 P1


dQ
Proof: By definition, S 
T
 mc v ln TT2  mc v ln T2  ln T1 
T2

dT
S  S 2  S1  mc v
T
T1 T 1

T P
S  S 2  S1  mc v ln 2  mc v ln 2
T1 P1

7. For steady-Flow work (WSF)  open system

WSF = V (P1 – P2)

Proof: By Law of Conservation of Energy,

Q = P + K + U + WF + WSF ; assuming P = K = 0

MRTC - 74
Multivector Review and Training Center

WSF = –WF = – (WF2 – WF1) = – (P2V – P1V) = P1V – P2V

WSF = V (P1 – P2)

Another proof: WF = WNF – WSF = - WSF

Therefore, WSF = – WF= – (P2V – P1V)
OR WSF = V(P1 – P2)

Isobaric Process – is an internally reversible process of a substance during which

the pressure remains constant.

P T
P=C
(V1,P) (V2,P) 2
T2
1 2
T1 1
WNF =  PdV P
Q

V S
V1 V2 – V1 S1 S2
V2

Formulas
1. Charle’s Law
P1V1 P2 V2 V1 V2
 OR 
T1 T2 T1 T2
where: P1 = P2

2. WNF = PdV = P(V2 – V1)

3. Q = H = H2 – H1 = mcp (T2 – T1)

Proof: Q = P + K + U + WF + WNF

Q = U + WNF
Q = U2 – U1 + P(V2 – V1) = U2 – U1 + PV2 – PV1
Q = (U2 + PV2) – (U1 + PV1)
But: H = U + PV
Therefore, Q = H2 – H1 = H = mcp (T2 – T1)

4. Change in internal energy (U)

U = U2 – U1 = mcv (T2 – T1)

MRTC - 75
Multivector Review and Training Center

5. Change in enthalpy (H)

H = H2 – H1 = mcp (T2 – T1)

6. Change in entropy (S)

T2 V
S  mcp ln  mcp ln 2
T1 V1


dQ
Proof: By definition, S  S 2  S1 
T
 
 mcp ln T T2  mcp ln T2  ln T1 
T2 dT
S  S 2  S1  mcp 
T
T1 T 1

T2 V2
S  S 2  S1  mcp ln  mcp ln
T1 V1

7. For steady-Flow Isobaric (WSF)  open system

WSF = 0 (if P = K = 0)

Proof: Q = P + K + U + WF + WSF

Q = H + WSF where: K + U = H = 0
WSF = 0

Another proof:
WF = WNF – WSF
P(V2 – V1) = P(V2 – V1) – WSF
Therefore, WSF = 0

Isothermal Process – is an internally reversible constant temperature process of a

substance.

P T
(V1, P1) PV = C 1 2
1
(V2, P2)
2
T Q
 PdV

V S
S1 S2 – S1
S2

MRTC - 76
Multivector Review and Training Center

Formulas
1. Boyle’s Law
P1V1 P2 V2
 OR P1V1  P2 V2
T1 T2
where: T1 = T2

 C ln V V2
V2
 
dV
WNF  PdV  C
V
2.
V1 V 1

 Cln V2  ln V1   C ln 2
V
V1
But C  P1V1  P2 V2 , also PV  mRT

V2 V V
Therefore, WNF  P1V1 ln  P2 V2 ln 2  mRT ln 2
V1 V1 V1
OR
P1 P P
WNF  P1V1 ln  P2 V2 ln 1  mRT ln 1
P2 P2 P2

3. U = 0
Proof: U = U2 – U1 = mcv (T2 – T1), since T1 = T2 = T

4. Q = WNF
Proof: Q = P + K + U + WF + WNF
Q = WNF

5. H = 0
Proof: H = H2 – H1 = mcp (T2 – T1)
H = 0


dQ Q V P
6. S   S 2  S1   mR ln 2  mR ln 1
T T V1 P2

proof: Based on the graph,

(S2 – S1) (T) = S (T) = Q

MRTC - 77
Multivector Review and Training Center

Therefore,
V2
mRT ln
Q V1 V2 P
S    mR ln  mR ln 1
T T V1 P2

7. Steady-Flow Isothermal (Open-System)

WSF = WNF = Q , ( if P = K = 0)
Proof: Q = P + K + U + WF + WSF
Q = WSF where: U + WF = H = 0
Therefore, WSF = WNF = Q
Another proof:
WF = WNF – WSF
P2V2 – P1V1 = WSF – WNF
Therefore, WSF = WNF = Q

Isentropic Process – is a reversible adiabatic process.

– constant entropy process.

Adiabatic – means no heat transferred.

P T
1
k
PV = C

 PdV
2
V S

Formulas:

1. P1V1k  P2 V2k  PjVjk  C

k 1
T2  V1 
2.  
T1  V2 
k
P2 V1k  V1 
Proof: P1V1k  P2 V2k ,   
P1 V2k  V2 

MRTC - 78
Multivector Review and Training Center

P1V1 P2 V2
But   mR
T1 T2
k k 1
T2 P2 V2  V1   V2   V1   V1 
       
T1 P1V1  V2   V1   V2   V2 

Therefore,
k 1
T2  V1 
 
T1  V2 

k 1
T2  P2  k
3.  
T1  P1 
P1V1 P2 V2 V1 P2  T1 
Proof:  ;   
T1 T2 V2 P1  T2 
k 1 k 1
T2 P2  T1  P  T1k  1
     2 
T1 P1  T2   P1  T2k  1
    P 
T2 T2k  1
k 1
T 
;  2 
1
 T2 
 
k 1
P 
  2 
k 1

   P 
2
k 1
T T 1 1 1  T1   T1   P1 
1
1
 T  kk k  1 
  k
 2     P2 
 
 T1  
   P1 

Therefore,
k 1
T2  P2  k
 
T1  P1 

4. WNF = PdV
V2

WNF  C V1
V2
k
V dV  C
V1  k 

1  k 

C
1k 2

V1  k  V11  k 
V1

CV21  k  CV11  k P2 V2k V21  k  P1V1k V11  k


1k 1k
P2 V2  P1V1 mRT2  mRT1

1k 1k

MRTC - 79
Multivector Review and Training Center

Therefore,
P2 V2  P1V1 mR T2  T1 
WNF    mc v T2  T1 
1k 1k
R cp
where: cv  , k , R  cp  c v
k 1 cv

5. U = mcv (T2 – T1)

Also, U = –WNF
Proof: U = mcv (T2 – T1) = –mcv (T1 – T2) = – WNF

6. Q=0
Proof: Refer to T-S diagram
Proof: By Law of Conservation of Energy
Q = P + K + U + WF + WNF
But U = –WNF
Therefore, Q = –WNF + WNF
Q=0

7. H = mcp (T2 – T1)

8. S = 0
Proof: Based on the graph, S2 = S1
S = S2 – S1 = 0

9. Steady Flow Isentropic (open-system)

WSF = –H , (if P = K = 0)
Proof: By Law of Conservation of Energy,
Q = P + K + U + WF + WSF where: U + WF = H
Therefore,
WSF = – H
Another proof:
WF = WNF – WSF
But WNF = –U

MRTC - 80
Multivector Review and Training Center

Therefore, WF = –U – W SF

WSF = – U – WF
WSF = – (U + WF)
WSF = – H

Polytropic Process – is an internally reversible process during which,

P T
n
PV = C 1
1
2
2
 PdV Q

V S

Formulas

1. P1V1n  P2 V2n  Pi Vin

n 1
T2  V1 
2.   ; refer to Isentropic process derivation
T1  V2 

n 1
T2  P2  n
3.   ; refer to Isentropic process derivation
T1  P1 

V1
4. WNF  PdV  C V2
V  ndV ; refer to Isentropic process derivation

P2 V2  P1V1 mR T2  T1 
WNF  
1n 1n

5. U = mcv (T2 – T1)

6. The heat transferred (Q),

Q = U + WNF = mcn (T2 – T1)
where: cn = polytropic specific heat

MRTC - 81
Multivector Review and Training Center

k n
cn  c v  
1n 
cp
k
cv
Proof: Q = P + K + U + WNF
Q = U + WNF
mR T2  T1 
Q  mc v T2  T1  
1n

But R = cv(k – 1)
Therefore,
mc v T2  T1 k  1
Q  mc v T2  T1  
1n
 k  1
Q  mc v T2  T1  1  
 1  n 
 k  1
Q  mT2  T1  c v  
1n
Q  mcn T2  T1 
H  mcp T2  T1 
dQ T
8. S  S 2  S1    mcn ln 2
T T1
Proof:
 mc n ln TT12
dQ T dT
S  S 2  S 1    mcn T 2
T
T 1 T
S  S 2  S1  mcn ln T2  ln T1   mcn ln 2
T
T1

9. Steady-Flow Polytropic (open system)

WSF = Q – H , if P = K = 0
Proof : By Law of Conservation of Energy,

Q = P + K + U + WF + WSF where: U + WF = H

Q = H + WSF
WSF = Q – H
Another proof: WF = WNF – WSF

MRTC - 82
Multivector Review and Training Center

From, Q = U + WNF where: WNF = H

WNF = Q – m U
Therefore, WF = Q – U – WSF
WSF = Q – U – WF
WSF = Q – (U + WF)
But H = U + WF
Therefore, WSF = Q – H

Second Law of Thermodynamics

In a heat engine running between two temperatures, higher temperature (T H) and
lower temperature (TL), it is impossible for the input energy at higher temperature
to be completely converted to work without rejecting some heat at (T L).

Heat Engine:
W = network = Wout – Win

Engine

QL
QH Output
Input Reservoir
Reservoir
TL
TH

By First Law of Thermodynamics,

Q = W OR Q = W
QH – Q L = W Qin – Qout = Wout – Win
W = QH – QL QH – Q L = Wnet

output
Efficiency ,   x 100%
input
W Q  QL  Q 
 x 100%  H x 100%   1  L  x 100%
QH QH  Q H 

MRTC - 83
Multivector Review and Training Center

For Carnot Cycle,

Q
 cons tan t  k
T
QL Q H QL TL
  k OR 
TL TH Q H TH

Hence, Carnot Efficiency

Wmax  Q   T 
max  x 100%   1  L  x 100%   1  L  x 100%
QH  Q H   TH 

Notes: 1. T must always expressed in absolute temperature scale (oR or K).

2. Q must always positive either absorbed or rejected in formulas in this
topic.

Heat Pump – is a refrigeration system that can be use to heat a house in winter and
cool it in summer.

Winter Time:

Input Output
Reservoir Reservoir
QL Heat QH
Pump

TL TH

W
QH
C. O . P . 
QL QH W

MRTC - 84
Multivector Review and Training Center

By first Law of Thermodynamics  sdd

Q = W
QL – Q H = – W
W  Q H  QL

Therefore,
QH
C. O. P. 
Q H  QL

For Ideal Heat Pump (Carnot Cycle)

Q
k
T
Q H QL
 k
TH TL
Q H  kTH , Also Q L  kTL
kTH
C. O. P. 
kTH  kTL
Therefore,
TH
C. O. P. 
TH  TL

For Carnot cycle,

QH QH TH
C. O. P.   
W Q H  QL TH  TL

Note: Typical C.O.P. range from 2 to 3

MRTC - 85
Multivector Review and Training Center

Summer Time
W

Output Input
Reservoir Reservoir
QH Heat QL
Pump

TH TL

QL
C. O. P. 
W

W GE

QH QL
W

QH QL

QL
C. O. P. 
W

By first Law of Thermodynamics

Q = W
QL – Q H = –W
W = QH – QL
Therefore,
QL
C. O. P. 
Q H  QL

For Carnot Cycle,

Q
k
T

MRTC - 86
Multivector Review and Training Center

Q H QL
 k
TH TL
TL
Hence, C. O. P. 
TH  TL

Also for Carnot Refrigerator/Ideal Refrigerator,

QL QL TL
C. O. P.   
W Q H  QL TH  TL

Energy Efficiency Ratio (EER)

 BTU 
Heat extracted per hour 
EER   hr   3.42 C. O. P.
Power consumptionwatts 

EER is expressed in unit of BTU per watt-hour.

MRTC - 87
Multivector Review and Training Center

MRTC - 88