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HEAT
If c1, c2, c3, ... cn are the velocities of the molecules of a gas at any instant, the mean square
2 velocity of the molecules of the gas is, c = 2 2 2 c1 +c2 +c3 + ... . Hence root mean square n
velocity of a molecule is
c rm =
2 2 2 2 c1 +c2 +c3 + ... c n n
time = 2m v
A D
Fig. 1.1
We shall now consider the combined effect of collisions of all molecules on the wall B. All the n molecules in the cubical vessel are not moving along the x-axis between the walls B and A. Since there are only three independent directions x, y and z, it is reasonable
Heat
Therefore, force exerted by the molecules on the walls B = m nv 2 . Being the area of the surface B is 1 sq. m., the pressure exerted on the wall B is
P= 1 m nv 2 3
But all molecules are not moving with the same velocity. Hence it is reasonable to substitute c 2 , the mean square velocity of the molecule, for v2. If c1, c2, c3, ... cn are the velocities of the molecules at any instant, then
2 2 2 2 c 2 = c1 +c2 +c3 + ... c n
Therefore,
1 P = m nc 2 3
Since m is the mass of the molecule and n is the number of molecules per unit volume of the gas, then
= mn 1
1 2 c 3
i.e. ,
P=
Further discussion is possible by choosing unit volume or molar volume (Vm). Let us consider one mole of a gas which occupies a volume Vm. The pressure exerted by the gas is
P=
PVm =
1 m N Ac 2 3 Vm
mc 2 =
3RT = 3k BT NA
as Boltzmann constant k B =
R . NA
or
1 3 m c 2 = k BT 2 2
...(1)
This is kinetic energy of a molecule. Hence, average kinetic energy of one mole of the gas is
1 3 3 m c 2 N A = N A k BT = RT 2 2 2 ...(2)
3 k BT or K.E. T. 2 Conclusion: Let us consider any amount of a gas. Let P, V, T and n be the pressure, volume, temperature and number of the molecules of the gas.
1 2 1 2 M c 2 = M c 2 = K .E . of the gas 3 3 2 3
2 3 nk BT 3 2
...(3)
or
PV = nk BT
...(4)
(ii) Since K.E. of the gas is proportional to the absolute temperature, from equations (3) and (4), PV T.
Conclusions
(a) At constant pressure [from Eqns. 3 and 4] V T. This is Charles first law (b) At constant volume P T. This is Charles second law.
Heat
J kg1 K1
4200 378 924
kJ kg1 K1
4.2 0.378 0.924
J gm1 K1
4.2 0.378 0.924
Water equivalent: Water equivalent of a body is the mass of water having the same heat capacity as the given body. In S.I. unit, water equivalent (in kg) =
Quantity of heat: If m is the mass of the body, C is the specific heat, then quantity of heat Q required to raise the temperature through is m C i.e. , Q=mC Method of mixtures: When a hot body is allowed to share its heat with a cold body, there is a flow of heat from the hot body to the cold body until both attain a common temperature. Then, if no heat is lost to or gained from the surroundings, then Heat lost by the hot body = Heat gained by the cold body.
dV
P V T
Fig. 1.2
Heat
Let P be its pressure, V its volume and T its temperature. Keeping the volume constant, let the gas be heated so as to raise its temperature by one degree kelvin. The quantity of heat supplied, Q = CV This amount of heat is used only to raise, the internal energy of the gas. Now, let us imagine the gas be heated at constant pressure so as to raise the temperature by 1 K. The quantity of heat supplied is given by Q = CP This amount of heat is partly used to raise the internal energy of the gas as the temperature raises by 1 K and also used to do external work as the gas expands to keep the pressure constant. Therefore, CP = CV + external work ...(1) When the gas expands keeping pressure cosntant, let the piston be moved through a distance dx. Hence external work done by the gas, W = F S = P A dx = PdV where A is the area of cross-section of the piston and A dx = dV is the increase in volume of the gas. Thus, equation (1) can be written as CP = CV + PdV ...(2) For an ideal gas, PV = RT After expansion, P (V + dV) = R (T + 1) i.e. , i.e. , or PV + PdV PV = RT + R RT PdV = R CP = CV + R CP CV = R
This is the well known Mayers relation. An Example: Let us consider air at constant pressure with CP = 966 J kg1 K1. Density of air at STP = 1.293 kg/m3. Get the value of R using PV = RT Pressure (STP) = 1.013 105 N/m2, T = 273 K, = 1.293 kg/m3. Gas constant for 1 kg,
R= R= PV P M 1 = as = = T T V V 1.013 10 5 1.293 273
R = 287 J kg K .
W =
V1 V2
Pd V ;
but PV = RT or P =
V2
RT V
Thus,
W =
V1
RT dV d V = RT . V V V
i.e. ,
V W = RT 2.303log 2 V1
P1V1 = P2V2 or P1 V2 = P2 V1
But
Adiabatic transformation: The process that takes place in a system under thermal isolation, such that heat is not transferred from the system to outside or from outside to a system is called an adiabatic process. It means that there is no exchange of heat between the system and surroundings. The expansion or compression of a gas enclosed in a perfectly non-conducting cylinder filled with a perfectly non-conducting frictionless piston. Since the system is thermally insulated no heat can enter or leave the system i.e., dQ = 0.
Heat
Hence dU + PdV = 0. Since perfect isolation is not practically possible, the physical changes should take place very rapidly so that heat produced during compression does not have enough time to leave the system and similarly during expansion heat does not have enough time to enter the system. When a certain mass of a perfect gas undergoes adiabatic changes, the total work done when the volume changes from V1 and V2 is
V2
W =
V1
Pd V
k V
Thus,
W =
V1
(k
V2
V )d V
W = k V d V =
V1
k 1 1 V2 V1 1
Again, Thus,
If the temperature of the gas changes from T1 to T2 during the operation, then
P1V1 = RT1 and P2V2 = RT2 W = R (T1 T2 ) 1
Conclusion: The simple relation of isothermal change is PV = k Differentiating this equation we get, PdV + VdP = 0
Pd V = Vd P
dP P = dV V
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V dP + P V 1d V = 0
If V = 1, we get
Vd P + P d V = 0
or
dP P = dV V
P V
That is under same conditions of pressure and volume, the slope of adiabatic curve is -times that of isothermal formation.
SHORT QUESTIONS
1 Mark Questions
1.1 1.2 1.3 1.4 1.5 1.6 Give the dependence of root mean square velocity on absolute temperature. Write down the relation connecting kinetic energy of a molecule, Boltzmann constant and absolute temperature. State Boyles Law. Give the unit of specific heat. What is Mayers relation? Dependence of K.E. of a molecule with temperature.
2 Mark Questions
1.1* 1.2 1.3 1.4* 1.5 1.6* 1.7 State two important postulates of kinetic theory of gases. Find the relation between PV and the kinetic energy of the gas. The quantities required to measure the amount of heat in an experiment. Explain. Explain Charles Law. Discuss the principle of method of mixtures. Two kilogram of water is heated to raise the temperature from 30 C to 40C. Compute the heat energy supplied in joule. Explain why CP > CV.
Heat
11
1.4* Since K.E. of the gas is proportional to the absolute temperature, PV T i.e., At constant pressure,V T. This is Charles first law. Similarly at constant volume P T. This is Charles second law. 1.6* The general formula for heat lost or heat gained is ms . In this case m = 2 kg, s = 4200 joule kg1 K1 and = (40 30)C. Thus, Q = m s = 2 4200 10 J Q = 84000 joule.
REVIEW QUESTIONS
10 Marks Questions
1.1 ( a ) Bring out the important postulates of kinetic theory of gases.
( b ) Obtain the expression for the pressure exerted by a gas in a cubical box in terms of the density of the gas and root mean square velocity. ( c) At STP, calculate the value of R using the equation PV = RT.
1.2 ( a ) Discuss the pressure exerted by a gas and obtain an expression for the pressure using kinetic theory of gases.
( b ) Derive the expression for kinetic energy of a gas. ( c) Deduce Boyles law and Charles laws.
1.3 ( a ) Explain specific heat of a gas at constant volume and constant pressure
( b ) Obtain Mayers relation. ( c) Explain why Cp > CV ? 1.4 ( a) Explain isothermal expansion and obtain the expression for the work done during this process. ( b ) Show that for an adiabatic change in a perfect gas, PV = constant. ( c) A quantity of dry air at 27C is compressed slowly to (1/3) of its original volume. What is the percentage change in pressure?
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Solution:
C P CV = R
CP = 1.66 or C P = 1.66C V CV
Thus
1.66 C V C V = R = C V ( 1.66 1) = R
CV =
Solution:
The mean K.E.,
1 3 m c 2 = k BT 2 2
or
1 3 3 m N A c 2 = N A k BT = RT 2 2 2
mN A = M A = 32 10 3
1 3 M A c 2 = RT 2 2
c =
3RT = MA
3 8.32 300 32 10 3
c = 4.83 10 2 m s Answer.
1.3 At what temperature, pressure remaining constant, the RMS velocity becomes double its value at T1 = 273 K. Let C1 and C2 be the velocities corresponding to T1 and T2.
Heat
13
Solution:
c2 T = 2 c1 T1 2c 1 T = 2 c1 T1
or
T2 =4 T1
Solution:
2 103 kg of hydrogen will have 6.02 1026 molecules. 10-3 will have
NA molecules. 2
E = 2010.6 J Answer.
1.5 Given CP = 24.65 J/mol-K for hydrogen. Find CV for hydrogen. R = 0.00831 kJ/ mol-K.
Solution:
C P CV = R
C V = C P R = 24.65 8.31
i.e. ,
C V = 16.34 J mol-K Answer.
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1.6 A quantity of air at 300 K and atmospheric pressure is suddenly compressed to half its original volume. Find the final pressure and temperature.
Solution:
(i) P1 = P2 = 1 = atmospheric pressure
V1 = V and V2 = V 2
P1V1 = P2V2
V P2 = P1 1 V2
= 1( 2 )
1.4
T1V11 = T2V21
T2 = T1 [ 2]
1.4 1
= 300 [ 2]
0.4
T2 = 395.9 K Answer.
1.7 Calculate the work done if one mole of an ideal gas expands isothermally at 127C until its volume is doubled [R = 8.13 J mol1 K1]. Express the answer in calorie.
Solution:
m = 1 mol, T = 400 K; V1 = V, V2 = 2V. Work done = RT log e (V2 V1 )
= 8.31 400 2.303 log 10 2
i.e. , or
W = 2.30 10 3 J
W = 2.30 10 3 = 0.54 10 3 calorie 42