CHAPTER 1: THERMODYNAMICS

Chapter 1 - Content

1.2 Thermodynamics
1.2.1. Mole
1.3 Ideal Gases
1.4 Real Gases

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1.2 Thermodynamics
Termo Heat, Dynamic Change
Thermodynamic is science of knowledge focusing on macroscopic
system as a result of the change of temperature
A study involving equilibrium properties of a system and
changes in equilibrium properties while the process is taking
place.

Thermodynamic system
1. Open transfer of matter/energy between system & surrounding
2. Close no transfer of matter between the two.
3. Isolated no transfer of matter & energy between the two.

surrounding

system
wall
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1.2 Thermodynamic (continue ..)
The wall is divided into 2 types:
a. Permeable / adiabatic (allows mass transfer / const. temp. due to
no transfer of heat)
b. Impermeable / nonadiabatic (no mass transfer / temp. changes &
transfer of heat due to conducting)
Equilibrium No macroscopic change in properties with time
a. Mechanical (force) no acceleration, no turbulent
b. Material no change, no chemical reaction
c. Thermal no change in temperature/heat
Thermodynamic properties
Extensive Intensive
a. Composition/conc. a. Mass (m) (independent of matter)
b. Volume b. Volume (V) a. Density, (m/V)
c. Pressure c. Force (F) b. Pressure, P (F/A)

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1.2 Thermodynamic (continue ..)

State function
If there is a change in pressure such that,
2
1
dP P2 P1
and/or that its cyclic path = 0,

dP 0
which is not affected by the path of a process, then pressure
is said to be the state function of the process.

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1.2 Thermodynamic (continue ..)
A method to determine whether a thermodynamic property is a
state function or not is by use of Eulers technique.
If, fxy = fyx
Then, the thermodynamic property is said to be the state
function.
Take the function V(T,P) = 3TP3+8T2P4 as an example,
fy = 9xy2+32x2y3
fyx = 9y2+ 64xy3
fx = 3y3+16xy4
fxy = 9y2+ 64xy3
Therefore, V is a state function. Other examples of state functions
include U, H, S and G.
Heat, q, and P-V work, w, is not a state function since its value
depends on the path of the process.
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1.2.1 Mol, n
Mass having elementary entity equivalent to Avagadro number
NA = 6.021023. Molar mass/molecular weight, M = m/n (g/mol)
where m is mass of substance and n is the number of moles.

1.3 Ideal gases

Equation of state (EoS), resulted from Boyle (PV = k)
& Charles (V T) laws
PV = nRT = mRT/M
z 1
P = RT/M

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1.3 Ideal gases (Continue ..)

Problem example:
Gas molecular weight of F2 is 38.0 g/mol. Calculate the density
(g/cm3) of the gas when it is operated at 20C and 188 torr.

Solution:
MP

RT
-1
(38.0 g.mol )(188 torr) 1 atm
1 1
(82.06 cm atm.mol K )(20 273.15)K 760 torr
3

3.9010-4 g.cm -3

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1.3 Ideal gases (Continue ..)

V 1 Vm
Thermal expansion coefficient, T , P
1

T P , n Vm T P
V
1 V 1 Vm
Isothermal compression, T , P
V P T , n Vm P T

RT Vm
PVm RT , Vm , R/P
P T
1 V 1 R
T , P m 1 / T
Vm T P Vm P

Vm
RT / P 2
P
1 Vm 1 RT
T , P 2 1/ P
Vm P T Vm P
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1.3 Ideal gases (Continue ..)
Problem example:
Methane inside a 1.0 L glass bulb at 10.0 kPa is connected to another
3.0L bulb containing H2 at 20.0kPa. Both bulbs remain at the same
temperature. Calculate,
a. Overall pressure after both gases are mixed
b. Mole fraction of each component gas.
Solution:
P1V1 Pi
a. P2 b. xi
V2 Ptotal

PH
20kPa3L
15kPa 15
2
4L xH2 0.857
17.5
PCH
10kPa1L
2.5kPa 2.5
4
4L xCH4 0.143
17.5
Ptotal 15 2.5kPa 17.5kPa
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Compressibility factor, z

For ideal gas, the compressibility factor, z = 1

= PM/(zRT)

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1.4 Real gases
2 H2
a 1 b
Z 1 b ..
RT Vm Vm

doi:10.1016/S0360-3199(00)00123-3

doi:10.1016/S0896-8446(03)00072-X

Can you find these charts from verifiable

literature/source? How would you refer them
in report/thesis? doi:10.1016/j.fluid.2005.03.020

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1.4 Real gases (Continue ..)
Van der Waals equation:

P a Vm b RT
2
Vm
Van der Waals constants:

2 2
27 R Tc
a
64 Pc
RTc
b
8Pc

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1.4 Real gases (Continue ..)

Van der Waals constants:

Gas a (L2bar.mol-2) b (L.mol-1) Gas a (L2bar.mol-2) b (L.mol-1)

H2 0.2476 0.02661 CH4 2.283 0.04278

He 0.03457 0.02370 C2H6 5.562 0.06380

N2 1.408 0.03913 C3H8 8.779 0.08445

O2 1.378 0.03183 C4H10 (n) 14.66 0.1226

Cl2 6.579 0.05622 C4H10 (iso) 13.04 0.1142

NO 1.358 0.02789 C5H12 (n) 19.26 0.1460

NO2 5.354 0.04424 CO 1.505 0.03985

H2O 5.536 0.03049 CO2 3.640 0.04267

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1.4 Real gases (Continue ..)

Critical constants:
Gas Tc (K) Pc (bar) Gas Tc (K) Pc (bar)
H2 33.2 13.0 CH4 190.6 46.0
He-4 5.2 2.27 C2H6 305.4 48.9
N2 126.2 34.0 C3H8 369.8 42.5
O2 154.6 50.5 C4H10 (n) 425.2 38.0
Cl2 417 77.0 C4H10 (iso) 408.1 36.5
Bromin 584 103.0 Ethylena 282.4 50.4
Ammonia 405.6 113.0 Propylena 365.0 46.3
H2O 647.1 220.5 CO2 304.2 73.8

Repeat the earlier problem example but this time for real methane
and hydrogen gases. What can you conclude?

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1.4 Real gases (Continue ..)

Where, 2
2

CO2 O2 T=303K
H2

1.5

zP H2( P )

zP T2H2( P )
1
zP CO2( P )

zP O2( P )

H2
ppc = pseudocritical pressure of the gas mixture 0.5
Tpc = pseudocritical temperature of the gas mixture
pci = critical pressure of component i in the gas mixture T=600K
Tci =critical temperature of component i in the gas mixture
yi =mole fraction of component i in the gas mixture.
0 0
5 10 1 10 1.5 10 2 10
8 9 9 9
0
1.01310 2 10
4 P 9
P ressure (psi)

Papay, J., 1968. A termelestechnologiai parameterek valtozasa a gastelepek muvelese

soran. OGIL Musz, Tud, Kuzl, Budapest, 267-273.
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1.4 Real gases (Continue ..)

Beggs, D.H., Brill, J.P., 1973. A study of two-phase flow in inclined pipes. J. Petrol.
Technol. 25 (5), 607-617.
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1.4 Real gases (Continue ..)

Kumar, N., 2004. Compressibility Factors for Natural and Sour Reservoir Gases by
Correlations and Cubic Equations of State (MS thesis). Texas Tech University,
Lubbock, Tex, USA, pp. 14-15, 23.
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1.4 Real gases (Continue ..)

Mahmoud, M., 2014. Development of a new correlation of gas compressibility factor

(Z-factor) for high pressure gas reservoirs. J. Energy Resour. Technol. 136 (1),
012903.
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1.4 Real gases (Continue ..)
Problem example:
Calculate molar volume of ethane gas at 350K and 70 bar
assuming:
a. Ideal
b. Real gas behavior.
Solution:
RT (0.083145 L bar K 1 mol 1 )(350 K)
a. Vm 0.416 L mol -1
P (70 bar)

a
b. P 2 Vm b RT , P
RT a
2
Vm b Vm
Vm
(0.08315)(350) 5.562
70
Vm 0.06380 Vm
2

Vm 0.23 L mol -1
Find Z. At what condition Z >1? How would you find
volume experimentally? 22
TASK 1 - GROUP
Using a spreadsheet,
1. Construct 2 curves of z factor versus pressure at different temperatures.
2. The curves can be from 2 of the equations derived by Papay, Beggs,
Kumar, Mahmoud, or Van der Wall.
3. Ensure that each group chooses different combination of the equations
4. Discuss the differences between different models with appropriate
literature surveys to support your claims.
5. Each member in the group MUST fill-in the peer review/evaluation form.
It can either be attached together with the report or give to me directly.

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