TD MODULE 5
TD MODULE 5
TD MODULE 5
A pure substance is one that has a homogeneous and invariable chemical composition
throughout. It may exist in more than one phase, but the chemical composition is the same
in all phases.
Thus, liquid water, a mixture of liquid water & water vapor & a mixture of ice and water are
all pure substances, as every phase has the same chemical composition.
However, a mixture of liquid air & gaseous air is not a pure substance since the composition
of liquid air is different from the composition of gaseous air & thus the mixture is no longer
chemically homogeneous. This is due to different components in air condensing at different
temperature at a specified pressure.
As heat is transferred to the water, the temperature increase, the specific volume increases
slightly and the pressure remains constant.
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A-B - At water is at 200C. From A to B temperature increases & specific volume increases
along the constant pressure line. At B water is at 100 0C.
B-C - At B water is at its saturation temperature of 1000C at 1 atm pressure. Additional heat
transfer results in a change of phase ie, some of the liquid becomes vapor, and during this
process pressure remains constant, but the specific volume increases considerably. The
amount of heat energy absorbed for changing phase from sutured liquid to saturated vapor is
called latent heat of vaporization. For 1 atm for water it is 2257.1 kJ/kg.
If a substance exists as liquid at the saturation temperature & pressure, it is called saturated
liquid. Thus at B water is saturated.
At a point between B & C, water exists as part liquid and part vapor at the saturation
temperature & pressure. Its quality is defined as the ratio of the mass of the vapor to the
total mass, ie
If a substance exists as vapor at the saturation temperature & pressure, it is called dry
saturated vapor or simply saturated vapor. Thus at C water exists as saturated vapor.
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C-D - Along CD the temperature is greater than saturation temperature. Then water is said
to exist as superheated vapor. Temperature & volume both increases during the process.
If the temperature of the liquid is lower than the saturation temperature for the existing
pressure, it is called either a sub cooled liquid (implying that the temperature is lower than
the saturation temperature for the given pressure) or a compressed liquid (implying that the
pressure is greater than the saturation pressure for the given temperature.)
The figure below shows the curves plotted for different pressure in a T – v diagram.
The saturated liquid points ‘B’ for different pressures is joined to get ‘saturated liquid line’.
Similarly all the saturated vapor points ‘C’ joined together will give ‘saturated vapor line’.
As the pressure increases, the saturation line is getting shorter & shorter and it will become
a point when the pressure is 22.09 MPa for the case of water. This point is represented as
‘N’ and is known as critical point. It is defined as the point at which the saturated liquid &
saturated vapor sates are identical.
At a pressure above the critical pressure, there will not be distinct phase change process.
Instead, the specific volume of the substance will continually increase & at all times there
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will be only one phase present. Eventually, it will resemble a vapor, but we can never tell
when the change has occurred. Above the critical state, there is no line that separates the
compressed liquid region and superheated vapor region. However it is customary to refer to
the substance as superheated vapor at temperatures above the critical temperature and as
compressed liquid at temperature below the critical temperature.
P-v DIAGRAM
Consider again the piston cylinder device containing water at 1MPa and 200C. Water at this
state exists as compressed liquid. Now the weights on top of the piston are removed one by
one so that the pressure inside the cylinder decreases gradually. Water is allowed to
exchange heat with the surrounding so that its temperature remains constant.
As the pressure decreases, the volume of water will increase slightly. When the pressure
reaches the saturation pressure at 200C, the water will start to boil. During this both
temperature and pressure remains constant, but the specific volume increases. Once the last
drop of liquid is vaporized, further reduction in pressure results in further increase in
specific volume.
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P-v INCLUDING SOLID PHASE
Consider a constant pressure line 1-2-3-4-5-6. At ‘1’ the substance is in solid state.
Absorbing heat at ‘2’it becomes saturated solid.
From 2 –3:
Saturated solid absorbing latent of fusion at constant temperature & pressure melts. At ‘3’ it
will be liquid at the same temperature as ‘2’. So between 2-3, it will be a mixture of solid &
liquid. At ‘3’ the liquid is known as saturated liquid with respect to solidification.
From 3- 4:
From 4-5:
So between 4-5 it will be a mixture of liquid & vapor. At ‘5’ the state is saturated vapor.
From 5-6:
At pressure below triple line substance cannot exist as liquid. Hence at these pressures the
solid phase directly changes to vapor phase without passing to liquid phase which is known
as sublimation.
P- T DIAGRAM
Consider a solid in state A. When the temperature increases but the pressure (which is less
than the triple point pressure) is constant, the substance passes directly from the solid to the
vapor phase.
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Along the constant pressure line EF, the substance passes from the solid to the liquid phase
at one temperature & then from liquid to vapor phase at a higher temperature.
Constant pressure line CD passes through the triple point and it is only at the triple point the
three phases may exist together in equilibrium.
At a pressure above the critical pressure, such as GH, there is no sharp destination between
the liquid & vapor phases.
WATER
Water has peculiarity that it contracts on melting from solid ice to liquid water. In other
words the specific volume of solid ice is more than liquid water.
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The fact that water expands upon freezing has vital consequences in nature. If water
contracted on freezing as most other substances do, the ice formed would be heavier than
the liquid water, & it would settle to the bottom of rivers, lakes & oceans instead of floating
at the top. The sun’s rays would never reaches these ice layers & the bottom of many rivers,
lakes and oceans would be covered with ice year round, seriously disrupting marine life.
P.v.T. SURFACE
All the points on the surface represent equilibrium states. A P-v diagram is just a projection
of the P-v-T surface on the P-v plane, and T-v diagram is nothing more than a bird’s eye
view of this surface.
T – s DIAGRAM
Consider the heating of 1 kg of ice at –50C to steam at 2500C, the pressure being maintained
constant at 1 atm. The entropy increases of the system in different regions are as given:
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1 –2:
2-3:
∆S = S3 – S2 = 334.96/273
3-4:
∆S = S4 – S3 = Cp ln T4/ T3
4 – 5:
The entropy increases, as water is vaporized at 1000C absorbing the latent heat of
vaporization (2257 kJ/kg).
∆S = S5 – S4 = 2257/273
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5-6:
At a particular pressure if sf the specific entropy of saturated water and sg is that of saturated
vapor. The entropy change of the system during the phase change from liquid to vapor at the
pressure is sfg = sg – sf.
The value of sfg decreases as the pressure increases, & becomes zero at the critical point.
Q) Show that for an ideal gas, the slope of the constant volume line on the T-s diagram is
more than that of the constant pressure line.
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By first law of thermodynamics
dq – dw = du
dq = dw + du ( a)
But, dq/T = ds
ie Tds = dq (b)
Tds = dw + du
dw = Pdv
du = CvdT
(T/s)v = T/ Cv (1)
Again enthalpy h = u + Pv
Differentiating,
dh = du + Pdv + vdP
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From equation (c),
du = Tds - Pdv
ie dh = Tds + vdP
But dh = CpdT
ie, the slope of the constant volume line passing through point A is steeper than that of the
constant pressure line passing through the same point.
Tds = dh – vdP
ie (h /s)P = T
This equation forms the basis of the h-s diagram of a pure substance.
The equation sates that slope of an isobar (constant pressure line) on the h-s coordinate is
equal to the absolute saturation temperature ‘Tsat’ at that pressure. If the temperature
increases, the slope of the isobar will increase.
The liquid vapor region for water is shown below. Dryness fraction lines (x1, x2, etc) are
also shown.
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REFERENCE STATE & REFERENCE VALUES (STEAM TABLE)
In steam tables, for water, the state of saturated liquid at 0.01 0C is taken as the reference
state, and the internal energy and entropy are assigned zero value at that state. The
refrigerates, such as ammonia and chlorofluro carbon R-12 & l –22, the reference state is
arbitrary taken as saturated liquid at -400 C, and the internal energy and entropy are assigned
zero value.
Not that some properties may have negative values as a result of the reference state chosen.
Some times different tables list different values for some properties at the same state as well
as a result of using a different reference state. However, in thermodynamics we are
concerned with the changes in properties, & the reference state chosen is of no consequence
in calculation as long as we use values from a single consistent set of tables and charts.
= mg / (mf + mg)
Consider a tank that contains a saturated liquid vapor mixture. The volume occupied by
saturated liquid is vf, & the volume occupied by saturated vapor is vg.
ie, V = Vf + Vg
V = mv
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A two phase system can be treated as homogeneous mixture for convenience.
vav = vf + x vfg
x = (vav - vf)/vg
If x = 0.6, it implies that 60% of the mass is vapor & 40% is liquid.
ie, mg = xmt ,
Q) Find the saturation temperature, the changes in specific volume and entropy during
evaporation, & the latent heat of vaporizations of steam at 1MPa.
Ans.
10*105 Pa = 10 bar
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tsat = 179.910C
vf = 0.001127 m3/kg
vg = 0.19444 m3/kg
sf = 2.1387 kJ/kg K
sg = 6.5865 kJ/kg K
Ans
tsat = 120.230C
From steam table, for P = 200 kPa & 2000C for superheated state.
Q) Determine the temperature of water at a state of P = 0.5 MPa and h = 2890 kJ/kg.
Ans
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ie the given h > hg
Water is superheated.
T0 C h kJ/kg
T1 = 200 h1 = 2855.4
T2 = 250 h2 = 2960.7
By linear interpolation
T = 216.40C
Q) Calculate the dryness fraction of steam which has 1.5kg of water in suspension with 50
kg of steam.
Ans.
mg = 50 kg, mf = 1.5 kg
x = mg /( mg+mf)
Q) A vessel having a volume of 0.6m3 contains 3kg of liquid water and water vapor mixture
in equilibrium at a pressure of 0.5 MPa. Calculate.
ii)Volume of vapour
Ans
vf = 0.00109 m3/kg
vg = 0.315 m3/kg
v = vf + x.vfg
ie, x = 0.532
Ans.
Mwater = 2 kg
twater= 250C
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Point 1-water at 250C
h = hf1 + x hfg
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Q) Find the specific volume, enthalpy and internal energy of wet steam at 18 bar, dryness
fraction 0.85.
Ans
vwet = vf + x vfg
hwet = hf + x.hfg
i. It is superheated at 4000C
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Ans
usup = hsup - Pvsup = 3248.7x 103– (20 x 105 x 0.511) =2946 kJ/kg
hwet = hf + x.hfg
vwet = vf + x vfg
Q) Find the entropy of 1kg of superheated steam at a pressure of 12 bar and a temperature of
2500C. Cp for steam 2.1 kJ/kgK.
Ans
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m = 1 kg, P = 12 bar, tsup = 2500C, Cp = 2.1 kJ/kgK
GAS MIXTURES
When two or more ideal gases are mixed, the behavior of a molecule is not influenced by
the presence of other similar or dissimilar molecules & therefore a non reacting mixture of
ideal gases also behave as an ideal gas. Hence the mixture will obey PV = nRuT.
DALTON’S LAW
The pressure of a gas mixture is equal to the sum of the pressure each gas would exert if it
existed alone at the mixture temperature and volume.
The pressure exerted by a component gas if it existed alone at the mixture temperature &
volume is known as partial pressure of that component.
Dalton’s law was re-formulated by Gibbs to include a second statement on the properties of
mixtures. The combined statement is known as the Gibbs – Dalton law. It states,
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The internal energy, enthalpy & entropy of a gaseous mixture are respectively equal to the
sum of the internal energies, enthalpies and entropies of the constituents which it could have
if each constituent occupies alone at the mixture volume and temperature.
mu = mAuA + mBuB
mh = mAhA + mBhB
ms = mAsA + mBsB
Let RA and RB be the characteristic gas constants for the constituent gases A and B.
PAV = mART
PBV = mBRT
Let Rm be the equivalent gas constant for the gas mixture. Applying the characteristic gas
equation for the mixture,
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PV/T = (mA + mB)Rm …………(2)
The volume of a gas mixture is equal to the sum of the volume each gas would occupy if it
existed alone at the mixture temperature & pressure.
The volume a component would occupy if it existed alone at the mixture T and P is called
the component volume or partial volume.
By Avogadro’s law the number of moles of any gas is proportional to the volume of the gas
at a given pressure and temperature.
Therefore the total number of moles in the vessel must equal the sum of the moles of the
individual constituents.
ie, n = nA + nB
Let Pm, Tm & Vm be the pressure, temperature and volume of the mixture.
By Dalton’s Law
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The partial pressure of component A, PA = (nARUTm) / Vm
By Amagat’s law
ie for ideal gas mixture, the pressure fraction, the volume fraction & mole fraction of a
component are identical.
ie, PA = xAPm
VA = xAVm
nA = xAnm
Gibbs theorem states that the total entropy of a mixture of gases is the sum of the partial
entropies.
Consider a mixture of inert ideal gas containing number of gases numbered as n 1, n2,
n3,…… nc. Let the partial entropies of the components be s1, s2,…… Sc,
Let us imagine that the component gases are separated from one another by suitable
partitions, all the gases being at the same temperature T & pressure P.
ie Si = nksk ………..(1)
dh = CpdT
PV = nRuT
V/T = (nRu)/P
ds = Cp (dT/T) - nRu(dP/P)
the entropy of the one mole of the Kth component gas at T & P.
Therefore Si = nk sK
After the partitions are removed, the gases diffuse into one another at the same temperature
& pressure. By Gibbs theorem the entropy of the mixture, S f is the sum of the partial
entropies, with each gas exerting its respective partial pressure.
Sf = Ru nk ( k – ln Pk)
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But Pk = xkP
A change in entropy due to the diffusion of any number of inert ideal gases is,
Sf - Si = Ru nk (– ln xk)
= - Ru nk ln xk
PV = nRuT = mRT
Since mole fractions are less than unity, (Sf – Si) is always positive.
Q) A mixture of idea gases consists of 4kg of N2 and 6kg of CO2 at a pressure of 4 bar and a
temperature of 200C. Find.
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γ for CO2 = 1.286 and for N2 = 1.4
Ans
n = m/M
n N2 = 4/28 = 0.1428
2) Mm = xA MA + xB MB
OR, Mm = mm/nm
R = Ru/M
ie, RA = Ru/MA
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4) PA = xA P
PN2 = xN2 P
PCO2 = xCO2 P
VA = (mARATm)/ Pm
VN2 = (mN2RN2Tm)/ Pm
VCO2 = (mCO2RCO2Tm)/ Pm
5) Vm = VA + VB
ρm = ρA + ρB OR ρ = m/Vm
ρm = 10/1.7 = 59 kg/m3
6) Cv = R/(γ – 1)
CVN2 = RN2/(γ – 1)
CVCO2 = RCO2/(γ – 1)
CP = Rγ/(γ – 1) = γ Cv
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CPN2 = RN2 γ/(γ – 1) = γCvN2
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