States of Matter - Thermodynamics
States of Matter - Thermodynamics
States of Matter - Thermodynamics
👉 Charle’s Law
( at
constant n and P )
( at constant n and V )
Graphical representation of Boyle’s Law
Graphical representation of Charles's Law
Graphical representation of Gay Lussac’s Law
👉 Avogadro’s law :
( at constant P
and T )
Solution
Pressure at the surface = 76 cm of Hg = 76x13·6 cm of H2O = 10·3 m of H2O
Applying P1 V1 = P2 V2,
(At surface) = (At 100 m depth)
10·3xV = 110·3xV2
V2 = 0·093 V = 9·3% of V
Q. Which curve shows Charles’ law?
A B
C D
Q. Which curve shows Charles’ law?
A B
C D
👉 If p1 , p2 , p3…..pn be the partial pressure of n gases
enclosed in a given vessel and P be the total pressure of
the gaseous mixture. Then by Dalton’s Law of partial
pressure.
P=p1+p2+ p3…..pn
Most probable velocity (Ump) Average velocity (Uav) Root mean square velocity (Urms)
Solution
P=?
V = 10-3 m3
M = 10-25 Kg
N = 1023
Q. The root mean square speeds at STP for the
gases H2,N2,O2 and HBr are in the order
Z>1 Z<1
👉Pressure correction
👉 Critical Volume :
It is the volume occupied by one mol of a gas at Tc and Pc
Vc = 3b
👉 Relation b/w Tc , Pc , and Vc
Q. Van Der Waals constant ‘a’ has the dimensions
of
A mol L-1
B atm L2 mol-2
C litre mol-1
D atm L mol-2
Q. Van Der Waals constant ‘a’ has the dimensions
of
A mol L-1
B atm L2 mol-2
C litre mol-1
D atm L mol-2
Solution
According to van der Waals equation,
Q. Using van der waals equation. Find the
temperature at which 3 moles of SO2 will occupy a volume
of 10 dm3 at a pressure of 1.52 MPa given : a = 678.88 dm3
KPa mole-1 and b = 5.6x10-2 dm3 mol-1
Q. Using van der waals equation. Find the temperature at
which 3 moles of SO2 will occupy a volume of 10 dm3 at a pressure of
1.52 MPa given : a = 678.88 dm3 KPa mole-1 and b = 5.6x10-2 dm3 mol-
1
Solution
∴
∴ (1581.0992) (9.832) = 3x8.314xT or T = 623.26 K
∴ the required temperature 623.26 K
States of Matter PYQ
A closed tank has two compartments A and B, both filled with oxygen
(assumed to be ideal gas). The partition separating the two compartments is
fixed and is a perfect heat insulator (Fig. 1). If the old partition is replaced by a
new partition which can slide and conduct heat but does not allow the gas to
leak across (Fig. 2), the volume (in m 3 ) of the compartment A after the
system attains equilibrium is ____. [2018 Adv]
Solution
The diffusion coefficient of an ideal gas is proportional to its mean free path and mean
speed. The absolute temperature of an ideal gas is increased 4 times and its pressure is
increased 2 times. As a result, the diffusion coefficient of this gas increases x times. The
value of x is .. [2016 Adv]
The diffusion coefficient of an ideal gas is proportional to its mean free path and mean
speed. The absolute temperature of an ideal gas is increased 4 times and its pressure is
increased 2 times. As a result, the diffusion coefficient of this gas increases x times. The
value of x is .. [2016 Adv]
Solution
A closed vessel with rigid walls contains 1 mole of and 1 mole of 92U238 air at 298 K.
Considering complete decay of 92U238 to 82Pb206 , the ratio of the final pressure to the
initial pressure of the system at 298 K is [2018 Adv]
A closed vessel with rigid walls contains 1 mole of and 1 mole of 92U238 air at 298 K.
Considering complete decay of 92U238 to 82Pb206 , the ratio of the final pressure to the
initial pressure of the system at 298 K is [2018 Adv]
Solution
If the value of Avogadro number is 6.023 x 10-23 mol -1 and the value of Boltzmann
constant is 1.38 x 10-23 J/K , then the number of significant digits in the calculated value
of the universal gas constant is [2014 Adv]
If the value of Avogadro number is 6.023 x 10-23 mol -1 and the value of Boltzmann
constant is 1.38 x 10-23 J/K , then the number of significant digits in the calculated value
of the universal gas constant is [2014 Adv]
Solution
To an evacuated vessel with movable piston un der ex ter nal pressure of 1 atm, 0.1 mole
of He and 1.0 mole of an unknown compound (vapour pressure 0.68 atm at 0°C ) are
introduced. Considering the ideal gas behaviour, the total volume (in litre) of the gases at
0°C is close to [2011]
To an evacuated vessel with movable piston under external pressure of 1 atm, 0.1 mole of
He and 1.0 mole of an unknown compound (vapour pressure 0.68 atm at 0°C ) are
introduced. Considering the ideal gas behaviour, the total volume (in litre) of the gases at
0°C is close to [2011]
Solution
Thermodynamics
System, surrounding and Universe
Boundary Surrounding
Surface that separates Rest of the universe
system from its
surroundings
System
Part of universe we are interested in
If the value of a physical quantity depends only upon the state of the system and
does not depend upon the path by which this state has been attained.
Examples :
Pressure, volume, temperature, internal energy, entropy, free energy.
Path Function:
Examples :
Heat, work, Heat capacities(Molar heat capacities, specific heat
capacities etc
Among the following, the intensive property is (properties
are):
A molar conductivity
B electromotive force
C resistance
D heat capacity
Among the following, the intensive property is (properties
are):
A molar conductivity
B electromotive force
C resistance
D heat capacity
Solution:
A Internal energy
B Heat capacity
C expansion work
D Molar enthalpy
Among the following, the state function(s) is(are) :
A Internal energy
B Heat capacity
C expansion work
D Molar enthalpy
Solution:
ΔU = Ufinal - Uinitial
Heat capacity
m
Heat and work
A d l
(l-x)
dW = F.dx
also F = PA
dW = PA.dx
V = (l - x)A
⇒ dV = -A.dx ⇒ dW =
- Pext.dV
Work done on the Heat absorbed
system +q
+W
System
Work done by the
system Heat released
-q
-W
First law of thermodynamics
U2 = U1 + q + W
so ΔU = (U2 - U1) = q + W
A 1
B 2
C 3
D 4
A system undergoes a process which absorbed 0.5 kJ of heat
and undergoing an expansion against external pressure of 1
atm, during the process change in internal energy is 300 J.
Then predict the change in volume (lit.)
A 1
B 2
C 3
D 4
Solution:
Reversible process
Sand
Pext = Pint ± dP
Irreversible process
Enthalpy
So dH = dU + d(PV)
H = enthalpy of system
U = internal energy of the system
P = pressure at the boundary of the system
and its environment
V = volume of the system
● Enthalpy of a system is defined as
H = U + PV
So dH = dU + d(PV)
A 43
B 57
C 42
D None of these
One mole of a non-ideal gas undergoes a change of state from
(1.0 atm, 3.0 L, 200 K) to (4.0 atm, 5.0 L. 250 K) with a change in
internal energy (ΔU) = 40 L-atm. The change in enthalpy of the
process in L-atm:
A 43
B 57
C 42
D None of these
One mole of a non-ideal gas undergoes a change of state from
(1.0 atm, 3.0 L, 200 K) to (4.0 atm, 5.0 L. 250 K) with a change in
internal energy (ΔU) = 40 L-atm. The change in enthalpy of the
process in L-atm:
Solution:
Isochoric process
V = constant
dV = 0 P
W=0
From first law of thermodynamics
ΔU = qv isochoric
Heat exchanged at V1 V
constant volume
Isobaric process
Pgas = constant
Since pressure of gas is defined during whole of the process and hence
the process must be reversible
So dW = -PextdV
= -Pgas dV Isobar
Pressure
W = P(Vf - Vi)
Volume
Isothermal process
dT = 0
P
For expansion of an ideal gas
ΔU = nCVΔT
Isotherm
ΔH = nCpΔT
ΔU and ΔH = 0
V1 V
Isothermal process
W = -ve
ΔU < 0
ΔT < 0
ΔU = W T2 <T1
Temperature ↓ cooling occurs
W = +ve
ΔU > 0
T2 >T1
Temperature ↑ heating occurs
Work done in adiabatic process
A Ar and He respectively
B He and H2 respectively
C O2 and H2 respectively
D H2 and He respectively
In figure, A and B are two adiabatic curves for two different
gases. Then A and B corresponds to :
A Ar and He respectively
B He and H2 respectively
C O2 and H2 respectively
D H2 and He respectively
Solution:
5 mole of an ideal gas expand isothermally and irreversible
from a pressure of 10 atm to 1 atm against a constant external
pressure of 1 atm wirr at 300 K is:
A –15.921 kJ
B –11.224 kJ
C –110.83 kJ
D None of these
5 mole of an ideal gas expand isothermally and irreversible
from a pressure of 10 atm to 1 atm against a constant external
pressure of 1 atm wirr at 300 K is:
A –15.921 kJ
B –11.224 kJ
C –110.83 kJ
D None of these
5 mole of an ideal gas expand isothermally and irreversible
from a pressure of 10 atm to 1 atm against a constant external
pressure of 1 atm wirr at 300 K is:
Solution:
A gas behaving ideally was allowed to expand
reversibly and adiabatically from 1 litre to 32 litre. It’s initial
temperature was 327°C. The molar enthalpy change (in J/mol)
for the process is:
A –1125 R
B –675
C –1575 R
D None of these
A gas behaving ideally was allowed to expand
reversibly and adiabatically from 1 litre to 32 litre. It’s initial
temperature was 327°C. The molar enthalpy change (in J/mol)
for the process is:
A –1125 R
B –675
C –1575 R
D None of these
A gas behaving ideally was allowed to expand
reversibly and adiabatically from 1 litre to 32 litre. It’s initial
temperature was 327°C. The molar enthalpy change (in J/mol)
for the process is:
Solution:
Match the column:
Match the column:
Ans: (A – r) ; (B – p) ; (C – s) ; (D – q)
Match the column:
Match the column:
Ans: (A – p, s) ; (B – q, r) ; (C – r) ; (D – s)
Solution:
One mole of an ideal gas at 300 K and 5 atm is
expanded adiabatically to a final pressure of 2 atm against a
constant pressure of 2 atm. Final temperature of the gas is :
A 270 K
B 273 K
C 248.5 K
D 200 K
One mole of an ideal gas at 300 K and 5 atm is
expanded adiabatically to a final pressure of 2 atm against a
constant pressure of 2 atm. Final temperature of the gas is :
A 270 K
B 273 K
C 248.5 K
D 200 K
Solution:
Entropy
Spontaneous Non-spontaneous
ΔSsurrounding =
∴ ΔSsurr =
But the law of conservation of energy
qsurr = - qsystem
ΔSsurrr =
Calculation of ΔSSystem
For ΔSsystem
State State
ΔS
A reversible B
ΔSirreversible
∴ ΔSirrev = ΔSrev
reversible path.
Second law of thermodynamics
Mathematically
A spontaneous process:
An equilibrium process:
Integration gives
● Isothermal process
Reversible and irreversible isothermal expansion and contraction
of an ideal gas
ΔSsys = nR ln
For surroundings
● Isobaric process
ΔU = CvΔT
ΔH = CpΔT = qp
ΔSsys = nCp ln
For surroundings
ΔSsurr = (for
Entropy change for an ideal gas in a thermodynamic process
● Isochoric process
ΔU = CvΔT = qv
ΔH = CpΔT
ΔSsys = nCv ln
For surroundings
ΔSsurr = (for
Entropy change for an ideal gas in a thermodynamic process
● Adiabatic process
ΔU = CvΔT
ΔH = CpΔT
For surroundings
D
When two mole of an ideal gas heated from 300 K
D
Solution:
Gibbs free energy
A system parameter to predict the spontaneity of chemical
reaction was introduced by Gibb’s so that entropy calculation
for the surrounding need not be carried out
Mathematically
G = H - TS
G1 = H1 - TS1 for the initial state
G2 = H2 - TS2 for the final state
∴ G2 - G1 = (H2 - H1) - T(S2-S1) Gibbs - Helmholtz
ΔG = ΔH - TΔS equation
Condition for the process to be spontaneous
ΔG = ΔH - T ΔS
ΔH T ΔS Conditions ΔG
ΔH ΔS ΔG Remarks
D
For the process, H2O(𝓁) → H2O(g) at T = 100C and 1 atmosphere
pressure, the correct choice is :
D
Solution:
Standard entropy of X2, Y2 and XY3 are 60, 40 and 50 JK–1 mol–1,
respectively.
For the reaction, 𝚫H = –30 kJ.
A 500 K
B 750 K
C 1000 K
D 1250 K
Standard entropy of X2, Y2 and XY3 are 60, 40 and 50 JK–1 mol–1,
respectively.
For the reaction, 𝚫H = –30 kJ.
A 500 K
B 750 K
C 1000 K
D 1250 K
Solution:
Two blocks of the same metal having same mass and at temperature
T1 and T2, respectively, are brought in contact with each other and
allowed to attain thermal equilibrium at constant pressure. The
change in entropy, 𝚫S, for this process is:
D
Two blocks of the same metal having same mass and at temperature
T1 and T2, respectively, are brought in contact with each other and
allowed to attain thermal equilibrium at constant pressure. The
change in entropy, 𝚫S, for this process is:
D
Solution:
Match the column:
Match the column:
Ans: (A) (p, s); (B) (r) ; (C) (q, s) ; (D) (q, s).
Solution:
Match the thermodynamic processes given under Column-I with the
expressions given under ColumnII.
Match the thermodynamic processes given under Column-I with the
expressions given under ColumnII.
Ans : 189494
Solution :
Benzene and naphthalene form an ideal solution at room
temperature. For this process, the true statement(s) is (are)
(2013 Adv.)
A ΔG is positive
B ΔS system is positive
C ΔS surroundings = 0
D ΔH = 0
Benzene and naphthalene form an ideal solution at room
temperature. For this process, the true statement(s) is (are)
(2013 Adv.)
A ΔG is positive
B ΔS system is positive
C ΔS surroundings = 0
D ΔH = 0
An ideal gas is allowed to expand from 1 L to 10 L against
a constant external pressure of 1 bar. The work done in
kJ is
(2019 Main)
A - 9 .0
B + 10.0
C -0.9
D -2.0
An ideal gas is allowed to expand from 1 L to 10 L against
a constant external pressure of 1 bar. The work done in
kJ is
Solution :
(2019 Main)
A - 9 .0
According to the given conditions, the expansion is against
B + 10.0 constant external pressure. So, the work done is given by following
formula;
C (a),(c)and (d)
C (a),(c)and (d)
A 150 mm of Hg
B 250 mm of Hg
C 350 mm of Hg
D 450 mm of Hg
4.4 g of a gas at STP occupies a volume of 2.24 L, the gas
can be
A O2
B CO
C NO2
D CO2
Calculate the weight of methane in a 9L cylinder at 16 atm
and 27℃?
Which one of the following equations does not correctly represent
the first law of thermodynamics for the given processes involving
an ideal gas? (Assume non- expansion work is zero)
A Cyclic process; q = -W
B Adiabatic process; ΔU = -W
C Isochoric process; ΔU = q
D Isothermal process; q = -W
1 mole of a monatomic gas expands adiabatically at initial
temp. ‘T’ against a constant pressure (external) of 1 atm from 1
L to 2 L. Find the final temp. of gas.
600 c.c. of a gas at a pressure of 750 mm of Hg is compressed
to 500 c.c. Taking the temperature to remain constant, the
increase in pressure, is
A 150 mm of Hg
B 250 mm of Hg
C 350 mm of Hg
Therefore increase of pressure
= (900 – 750) = 150 mm of Hg
D 450 mm of Hg
4.4 g of a gas at STP occupies a volume of 2.24 L, the gas
can be
C NO2
D CO2
Calculate the weight of methane in a 9L cylinder at 16 atm
and 27℃?
Solution
Which one of the following equations does not correctly represent
the first law of thermodynamics for the given processes involving
an ideal gas? (Assume non- expansion work is zero)
D Isothermal process; q = -W
1 mole of a monatomic gas expands adiabatically at initial
temp. ‘T’ against a constant pressure (external) of 1 atm from 1
L to 2 L. Find the final temp. of gas.
Solution