Chapter#2: Properties of pure substances

PURE SUBSTANCE
1. A substance that has a fixed chemical composition throughout is called pure substance.
2. Example:
a. Liquid water
b. Liquid water and ice
c. Liquid water, and steam
d. Gases (N2, CO2)
e. Air
3. Following are not the pure substances:
a. Oil + water
b. Air unmixed with water
c. Steam with impurities

PHASES
(a) Solid (b) Liquid (c) Gas

PHASES OF WATER
a) Compressed liquid or subcooled liquid (not about to
vaporize)
b) Saturated liquid (about to vaporize)
c) Saturated or vapor-liquid mixture (liquid and vapor
phases co-exist)
d) Saturated vapors (about to condense)
e) Superheated vapors (not about to condense)

PROBLEM
What is the difference between gas, vapors and steam?

SATURATION TEMPERATURE AND PRESSURE

Saturation temperature (Tsat)
1. It is the temperature at which a pure substance changes its phase.
2. Example:
a. Water boils at 100°C (Tsat) at P = 1 atm
b. Water boils at 250°C (Tsat) at P = 4 atm

Saturation pressure (Psat)

3. It is the pressure at which a pure substance changes its phase.
4. Example:
a. Water boils at 1 atm (Psat) at T = 100°C
b. Water boils at 0.0068 atm (Psat) at T = 30°C

Handouts for Thermodynamics 2

 Chapter#2: Properties of pure substances

LATENT HEATS
The amount of heat absorbed or released during phase-change process is called latent heat.

Latent heat of fusion

It is the heat which is absorbed during melting or released during freezing of a pure substance.
E.g. latent heat of fusion for water is (approx..) 333 kJ/kg at 1 atm.

ICE  LIQUID

Latent heat of vaporization (hfg)

It is the heat which is absorbed during vaporization or released during condensation of a pure substance.
E.g. latent heat of vaporization for water is (approx..) 2257 kJ/kg at 1 atm.

LIQUID VAPORS

PROPERTY DIAGRAM FOR THE PHASE-CHANGE PROCESS (WATER)

1. Higher is the pressure (P):

a. higher is saturation temperature (Tsat)
b. more is specific volume of saturation liquid
c. less is specific volume of saturation vapors
2. At critical point where Pcr=22.09 MPa and Tcr=375.14°C, saturation liquid and saturation vapors
states are identical i.e. vcr = 0.003155 m3/kg.

Handouts for Thermodynamics 3

 Chapter#2: Properties of pure substances

T-v and P-v property diagrams

Handouts for Thermodynamics 4

 Chapter#2: Properties of pure substances

P-V DIAGRAM EXTENDING TO INCLUDE SOLID PHASE

For substances that contracts on cooling

For substances that expand on cooling (e.g. water)

1. On a triple line, all three phases co-exist

2. If the pressure is lower than triple line, sublimation will occur.

Handouts for Thermodynamics 5

 Chapter#2: Properties of pure substances

P-T diagram

1. TTP = Triple point temperature PTP = Triple point pressure

2. TTP and PTP are inherent property of a pure substance
3. For water: TTP = 0.01°C and PTP = 0.6113kPa
4. Special case of dry-ice (CO2): It has triple point pressure (517 kPa) higher than atmospheric pressure
(101 kPa) so it sublimates (i.e. change its phase from solid to vapors directly, without getting
liquefied).

PROBLEMS
1. A pure substance has triple point pressure 0.3bar. It is placed in a chamber where the pressure is
0.01bar and a temperature is such that it is in solid phase. On heating, it first melts and then vaporizes.
Is it possible?
2. A pure substance melts at T=400°C and then vaporize at 340°C at a pressure higher than triple point
pressure. Is it possible?
Answer to both the problems is No.

ENTHALPY
1. The total heat content of a system is called enthalpy.
2. It is a combination property.

H = U + PV [kJ]
h = u + Pv [kJ/kg]

Handouts for Thermodynamics 6

 Chapter#2: Properties of pure substances

PROPERTY TABLES
Subscripts: f = fluid or liquid g = gas or vapors fg = g – f

A-4: For saturated liquid and saturated vapor states when T is given
A-5: For saturated liquid and saturated vapor states when P is given
A-6: For superheated water
A-7: For subcooled water (optional)

Linear interpolation
Y = (Y2 – Y1)/(X2 – X1) x (X-X1) + Y1

SATURATED LIQUID AND SATURATED VAPOR STATES

Use property tables A-4 and A-5

PROBLEM
A rigid tank contains 50 kg of saturated liquid water at 90°C. Determine pressure in the tank and volume
of tank.

Solution:

m = 50 kg T = 90°C State: Saturated liquid

P = Psat@T=90°C = ? V=?

P = Psat@T=90°C = 70.14 kPa

V = m.v = m . vf@T=90°C = 50 x 0.001036 = 0.0518 m3

PROBLEM
A mass of 200 g of saturated liquid water is completely vaporized at a constant pressure of 100 kPa.
Determine the volume change and the amount of energy added to water.

Solution:

m = 0.2 kg P = 100 kPa

States: (1) = Saturated liquid (2) = Saturated vapors

∆V = ? ∆H = ?

∆V = V2 – V1 = m(v2-v1) = m(vg - vf) = m.vfg = m.vfg@P=100kPa = 0.2 x 1.6930

= 0.3386 m3

∆H = H2 – H1 = m(h2-h1) = m(hg - hf) = m(hg@P=100kPa – hf@P=100kPa )= 451.6 kJ

Note: hfg is called enthalpy of vaporization or latent heat of vaporization.

Handouts for Thermodynamics 7

 Chapter#2: Properties of pure substances

SATURATED LIQUID-VAPOR MIXTURE (VLM)

Use property tables A-4, A-5 and quality.

Quality
1. It defines the mass of vapors present in a VLM state.
2. x = mvapor / mtotal = mvap / ( mvap + mliq) = mg / (mg + mf) = mg / mt
3. The value of x is in between 0 and 1.
x = 0 means saturation liquid x = 1 means saturation vapors

Average properties
The liquid and vapors in VLM states are mixed so well that they form a
homogeneous mixture. Therefore, their properties can be taken as
average.

Such that yav = yf + x.yfg and Yav = mt.yav

Also Yf = mf.yf Yg = mg.yg Yav = Yf + Yg
Where yf yav yg

Examples: vav = vf + x.vfg hav = hf + x.hfg uav = uf + x.ufg

PROBLEM
What is specific volume of water at 100°C and 30% quality?

Hint:

Find vf and vg at 100°C from Table A-4 and then calculate vav at x = 0.3.

PROBLEM
At some constant temperature, if vf = 0.002 m3/kg, vg = 0.2 m3/kg and vav = 0.11 m3/kg, calculate x and
plot state on T-v diagram.

Solution:

x = (0.11 – 0.002) / (0.2 – 0.002) = 54%

PROBLEM
A rigid tank contains 10 kg of water at 90°C. If 8 kg of water is in liquid form and the rest is in vapor
form, determine pressure in the tank and volume of tank.

Solution:

mt = 10 kg mf = 2 kg
mg = 8 kg and x = mg / mt = 0.2
T = 90°C State: VLM

P=? V=?

Handouts for Thermodynamics 8

 Chapter#2: Properties of pure substances

P = Psat@T=90°C = 70.14 kPa

V = mt . vav
where, vav = vav@x=0.2 = vf@T=90°C + x . vfg@T=90°C = 0.001036 + 0.2 x (2.359964) = 0.473 m3/kg

Hence, V = 10 x 0.473 = 4.73 m3

SUPERHEATED WATER
Use property table A-6.
Given problem must be satisfying the following conditions:
T > Tsat (at given P)
P < Psat (at given T)
v > vg, h > hg, u > ug (at given Tsat and Psat)

PROBLEMS
1. v = ? at T = 100°C and P = 0.05 MPa (Ans: 3.4187 m3/kg)
2. v = ? at T = 900°C and P = 7 MPa (Ans: 0.076750 m3/kg)
3. h = ? at T = 350°C and P = 0.01 MPa (Ans: 3178.35 kJ/kg)

P = 0.01 MPa (common)

T (known) h (required)
300 3076.7
350 (3076.7 + 3280)/2
→in mid = 3178.35
400 3280

4. u = ? at T = 250°C and P = 0.35 MPa

5. v = ? at T = 450°C and P = 0.7 MPa

Handouts for Thermodynamics 9

 Chapter#2: Properties of pure substances

6. h = ? at T = 850°C and P = 9.5 MPa

7. v = ? at T = 110°C and P = 0.01 MPa

8. h = ? at T = 430°C and P = 0.7 MPa

9. P = ? at v = 10.828 m3/kg and T = 900°C

10. T = ? at P = 0.7 MPa and h = 3059.45 kJ/kg

11. T = ? at P = 11 MPa and u = 2920 kJ/kg

Handouts for Thermodynamics 10

 Chapter#2: Properties of pure substances

PROBLEM
What is the phase and temperature of water at 0.5 MPa and 2890 kJ/kg enthalpy.

Solution:

As state is unclear therefore, a check is required.

h = h@p=0.5MPa = 2890 kJ/kg
hg = hg@P=0.5MPa = 2784 kJ/kg
As h > hg therefore, state is superheated vapors.

(Solve further)

COMPRESSED LIQUID WATER

Use property table A-7.
Given problem must be satisfying the following conditions:
T < Tsat (at given P)
P > Psat (at given T)
v < vf, h < hf, u < uf (at given Tsat and Psat)
Approximation: y = yf@T (use table A-1)

PROBLEM
P = 8 MPa T = 65°C h=?

(Answer: 278.68 kJ/kg)

PROBLEM
Determine the internal energy of compressed liquid water at 80°C and 5 MPa using (a) data from
compressed liquid tables (b) data from saturated liquid tables. Also calculate error involved.

Solution:

(a) u = u@T=80°C,P=5MPa = 333.82 kJ/kg

(b) u = uf@T=80°C = 334.97 kJ/kg

Error = (334.97 - 333.82 ) / 333.82 x 100 = 0.34% < 1% !!!

Handouts for Thermodynamics 11

 Chapter#2: Properties of pure substances

CONSTANT SPECIFIC VOLUME HEATING

Hint: P = const. or T = const. is not mentioned.

PROBLEM
A rigid tank with a volume of 2.5m3 contains 5 kg of saturated liquid-vapor mixture of water at 75°C.
Now, the water is slowly heated. Determine the temperature at which the liquid in the tank is completely
vaporized. Also, show the process on a T-v diagram.

Solution:

V = 25 m3 m = 5 kg => v = 2.5/5 = 0.5 m3/kg

T = Tsat@vg=v=0.5 = ?

(Answer: 140.7 °C)

IDEAL GAS EQUATION OF STATE

Equation of state
1. Any equation which relates pressure, temperature and specific volume of a substance is called
equation of state.
2. Example:
a. Ideal gas equation of state
b. Van der Waals equation of state
c. Beattie-Bridgeman equation of state
d. Benedict-Webb-Rubin (BWR) equation of state
e. Viral equation of state

Ideal gas equation of state

Pv = RT

Where,
P = Absolute pressure [Pa]
T = Absolute temperature [K]
R = Gas constant = Ru / M [kJ/kgK]
Ru = Universal gas constant = 8.314 kJ/kmolK
M = Molar mass (e.g. N2 = 28 kg/kmol)
Note: See Table A-1 for values of R and M. Be careful about unit consistency.

Ideal gas equation between two states

P1 V1 / T1 = P2 V2 / T2

Ideal gas
1. It is an imaginary substance

Handouts for Thermodynamics 12

 Chapter#2: Properties of pure substances

2. Real gases at low densities (Low pressure and high temperature) behaves close to ideal gas.
3. Water vapor at pressure less than 10 kPa, regardless of any temperature can be treated as ideal gas.

PROBLEM
Determine the mass of air in a room having dimensions 4m x 5m x 6m at 100 kPa and 25°C. Treat air as
an ideal gas with R=0.287 kPa.m3/kgK

Pv = RT => PV = mRT => m = PV/RT = … = 140.3 kg

SPECIFIC HEATS
Specific heat
1. It is the amount of specific energy required to raise the temperature of a substance by 1°C.
2. Unit: kJ/kgK or kJ/kg°C
3. It is a strong function of material and temperature.

Specific heat at constant pressure (Cp)

1. If the process is executed at constant pressure then, the amount of specific energy required to raise the
temperature of a substance by 1°C is called specific heat at constant pressure.
2. For example in open systems
3. Denoted by Cp = (∂h/∂T)p

Derivation:
ein – eout = esys
ein –eout = du + P.dv
CpdT = dh
Cp = (dh/dT)p

Also, h2 – h1 = h = Cp(T) dT

Specific heat at constant volume (Cv)

1. If the process is executed at constant volume then, the amount of specific energy required to raise the
temperature of a substance by 1°C is called specific heat at constant volume.
2. For example in close systems
3. Denoted by Cv = (∂u/∂T)v

Derivation:
ein – eout = esys
ein –eout = du
CvdT = du
Cv = (du/dT)v

Also, u2 – u1 = u = Cv(T) dT

Handouts for Thermodynamics 13

 Chapter#2: Properties of pure substances

Specific heats relation

We know,
h = u + Pv
h = u + RT
dh = du+ RdT
Cp dT = Cv dT + R dT
Cp = Cv + R

Hence,
Cp > Cv

Specific heat ratio

k = Cp / Cv

REMEMBER
For air: Cp = 1.005 kJ/kgK R = 0.287 kJ/kgK Cv = 0.718 kJ/kgK k = 1.4

Handouts for Thermodynamics 14