This PDF Is The Sample PDF Taken From Our Comprehensive Study Material For IIT-JEE Main & Advanced
This PDF Is The Sample PDF Taken From Our Comprehensive Study Material For IIT-JEE Main & Advanced
This PDF Is The Sample PDF Taken From Our Comprehensive Study Material For IIT-JEE Main & Advanced
INTRODUCTION
Thermodynamics is the branch of chemistry that deals with energy changes occuring during various physical
& chemical processes. It also deals with the transformation between different forms of energy.
TYPES OF SYSTEM
Depending on Exchange of Energy Between System and Surroundings System can be Classified as:
(i) Open System : A system which can exchange both energy and matter with surrounding.
(ii) Closed System : A system which can exchange only energy with surrounding.
(iii) Isolated System : A system which cannot exchange matter or energy with surrounding.
Boundary : Anything which separates system and surrounding is called boundary. Across boundary energy
and mass are transferred between system and surrounding.
A boundary can be real or hypothetical.
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THERMODYNAMICS
Hence heat exchanged at constant pressure and volume are important Definite quantities
Heat Capacity
The heat capacity of a system may be defined as the amount of heat required to raise the temperature of the system
by one degree.
If q is the small quantity of heat added to the system, let the temperature of the system rises by dT, then heat
capacity C of the system is given by
dq
C= .....(i)
dT
In case of gases we have two types of heat capacity i.e. heat capacity at constant volume and heat capacity at
constant pressure.
Heat Capacity at Constant Volume ( Cv )
Molar heat capacity at constant volume is defined by the relation
dq v
CV = ....(ii)
dT
For first law of thermodynamics
dU = dq – dw
But dw = P dV
dU = dq – P dV ....(iii)
At constant volume
dU = dqv
Heat capacity at constant volume Cv is given by
dq v U
Cv = dT T
v
U
or Cv = .....(iv)
T v
It may be defined as the rate of change of internal energy with temperature at constant volume.
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THERMODYNAMICS
P T – P2T1
w = –Pext × V = –Pext × (V2 – V1) = – Pext × R 1 2
P1P2
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THERMODYNAMICS
SOLVED EXAMPLES
Ex. 1 During 200J work done on the system, 140 J of heat is given out. Calculate the change in internal energy.
Sol. w = 200 J; q = –140 J;
q = E + (–w); where –w is work done by the system
E = q + w
E = –140 + 200 = +60J
Ex. 2 A gas absorbs 200 J of heat and expands against the external pressure of 1.5 atm from a volume of 0.5 litre. Calculate
the change in internal energy.
Sol. w = –PV = –1.5 × (1.0 – 0.5) = –0.75 litre atm
= –0.75 × 101.3 J = –75.975 J
1 litre atm = 101.3 J
Now, E = 200 – 75.975 = +124.025 J
Ex. 3 Two litre of N2 at 0oC and 5 atm pressure are expanded isothermally against a constant external pressure of 1 atm
until the pressure of gas reaches 1 atm. Assuming gas to be ideal, calculate work of expansion.
Sol. Since the external pressure is greatly different from the pressure of N2 and thus, process is irreversible.
w = –Pext (V2 – V1)
w = –1 × (V2 – V1)
Given V1 = 2 litre V2 = ? T = 273 K
P1 = 5 atm P2 = 1 atm
P1V1 = P2V2
2 5
V2 = = 10 litre
1
w = –1 × (10 – 2) = –8 litre atm
8 1 .9 87 8 1 .9 87 4 .1 8 4
calorie J = –810.10 joule
0.08 21 0 .0 82 1
Ex. 4 The enthalpy of vaporisation of liquid diethyl ether –(C2H5)2O, is 26.0 kJ mol–1 at its boiling point (35.0ºC). Calculate
S for conversion of : (a) liquid to vapour, and (b) vapour to liquid at 35ºC.
H vap. 26 10 3
Sol. (a) Svap. = 84.41 J K 1 mol1
T 308
H cond. 26 10 3
(b) Scond. = ( Hcond = –26 kJ)
T 308
= –84.41 JK–1 mol–1
Ex. 5 Calculate the free energy change when 1 mole of NaCl is dissolved in water at 25ºC. Lattice energy of NaCl = 777.8
kJ mol–1 ; S for dissolution = 0.043 kJ mol–1 and hydration energy of NaCl = –774.1 kJ mol–1.
Sol. Hdissolution = Lattice energy + Hydration energy
= 777.8 – 774.1 = 3.7 kJ mol–1
Now G = H – TS
= 3.7 – 298 × 0.043 = 3.7 – 12.814
G = –9.114 kJ mol–1
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THERMODYNAMICS
1. Out of boiling point (), entropy (), pH () and e.m.f. of a cell (V), intensive properties are :
(A) , (B) , , (C) , , V (D) All of the above
5. A gaseous system changes from state A (P1, V1, T1) to B (P2, V2, T2), B to C (P3, V3, T3) and finally from C to A. The
whole process may be called :
(A) Reversible process (B) Cyclic process
(C) Isobaric process (D) Spontaneous process
6.
I
II
P III
IV
V
The plots between P and V which represent adiabatic and isothermal process respectively :
(A) I, IV (B) II, III (C) III, II (D) IV, I
7. Five moles of a gas is put through a series of changes as shown graphicallay in a cyclic process the A B,
B C and C A respectively are A B
(A) Isochoric, Isobaric, Isothermal
(B) Isobaric, Isochoric, Isothermal
Volume
8. Determine which of the following reactions at constant pressure represent surrounding that do work on the system
I. 4NH3 (g) + 7O2 (g) 4NO2 (g) + 6H2O (g)
II. CO (g) + 2H2 (g) CH3OH ( )
III. C (s, graphite) + H2O (g) CO (g) + H2 (g)
IV. H2O (s) H2O ( )
(A) III, IV (B) II and III (C) II, IV (D) I and II, IV
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THERMODYNAMICS
4. P-V plot for two gases (assuming ideal) during adiabatic processes are given in the figure. Plot A and plot B should
correspond respectively to :
P
A
B
V
(A) He and H2 (B) H2 and He (C) SO3and CO2 (D) N2 and Ar
5. During the isothermal expansion of an ideal gas :
(A) The internal energy remains unaffected (B) The temperature remains constant
(C) The enthalpy remains unaffected (D) The enthalpy increases
5
6. 0.5 mole each of two ideal gases A C v,m = R and B (Cv, m = 3R) are taken in a container and expanded reversibly
2
and adiabatically, during this process temperature of gaseous mixture decreased from 350 K and 250 K. Then for the
process :
(A) U = – 100 R (B) U = – 275 R (C) H = – 375 R (D) H = – 300 R
7. When some potential difference V is applied across a resistance R then the work by the electrical field on the charge
q to flow through the circuit in time t will be :
V 2t
(A) qV (B) Vit (C) i2Rt (D)
R
8. When a liquid solidifies, generally, there is :
(A) Decrease in enthalpy (B) Decrease in entropy (C) Increase in enthalpy (D) Increase in entropy
9. Choose the correct statement (s) :
(A) Temperature, enthalpy and entropy are state functions
(B) For reversible and irreversible both isothermal expansion of an ideal gas, change in internal energy and
enthalpy is zero
(C) for a reaction in which n 2 = 0, entropy change is not always zero
P1
(D) The entropy change associated with reversible isothermal expansion of an ideal gas is equal to 2.303 R log10
P2
10. One mole of an ideal diatomic gas (Cv = 5 cal) was transformed from initial 25°C and 1 L to the state when temperature
is 100°C and volume 10 L. Then for this process(R = 2 calories/mol/K) (take calories as unit of energy and kelvin for temp)
373
(A) H = 525 (B) S = 5 ln + 2 ln 10
298
(C) E = 525 (D) G of the process can not be calculated using given information.
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CHEMISTRY FOR JEE MAIN & ADVANCED
1. Columm-I Columm-II
V2
(A) Reversible isothermal expansion of an ideal gas (p) w = –2.303 nRT log
V1
(B) Reversible adiabatic compression of an ideal gas (q) PV = constant
nR
(C) Irreversible adiabatic expansion of an ideal gas (r) w = ( 1) (T2 – T1)
(D) Irreversible isothermal compression of an ideal gas (s) H = 0
2. Column I Column II
(A) A process carried out infinitesimally slowly (p) Adiabatic
(B) A process in which no heat enters or leaves the system (q) G = 0
(C) A process carried out at constant temperature (r) Sublimation
(D) A process in equilibrium (s) E = 0, H = 0
(E) A(s) A(g) (t) Reversible
(F) Cyclic process (u) Isothermal
3. Columm - I Columm - II
(A) (Gsystem) T,P = 0 (p) Process is in equilibrium
(B) Ssystem + Ssurrounding > 0 (q) Process is nonspontaneous
(C) Ssystem + S surrounding < 0 (r) Process is spontaneous
(D) (Gsystem) T,P > 0 (s) System is unable to do useful work
4. Columm - I Columm - II
(A) Reversible adiabatic compression (p) Ssystem > 0
(B) Reversible vaporisation of liquid (q) Ssystem < 0
(C) 2N(g) N2(g) (r) Ssurrounding < 0
(D) MgCO3(s) MgO(s) + CO2(g) (s) Ssurrounding = 0
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CHEMISTRY FOR JEE MAIN & ADVANCED
1. In which of the following changes at constant pressure is work done by system on surrounding ? By the surrounding
on system ?
Initial state Final state
(ii) H2O (g) H2O()
(ii) H2O (s) H2O(g)
(iii) H2O () H2O(s)
(iv) 3H2 (g) + N2(g) 2NH3(g)
(v) CaCO3 (s) CaO (s) + CO2(g)
2. The gas is cooled and loses 65 J of heat. The gas contracts as it cools and work done on the system equal to
20 J which is exchanged with the surroundings. What are q, w and E ?
3. The enthalpy of combustion of glucose is –2808 kJ mol–1 at 25°C. How many grams of glucose do you need to
consume [Assume wt = 62.5 Kg].
(a) To climb a flight of stairs rising through 3m.
(b) To climb a mountain of altitude 3000 m ?
Assume that 25% of enthalpy can be converted to useful work.
4. What is E when 2.0 mole of liquid water vaporises at 100°C ? The heat of vaporisation, (H vap.) of water at
100°C is 40.66 kJ mol–1.
5. If 1.0 kcal of heat is added to 1.2 L of O2 in a cylinder of constant pressure of 1 atm, the volume increases to
1.5 L. Calculate E and H of the process.
6. When the following reaction was carried out in a bomb calorimeter, E is found to be –742.7 kJ/mol of NH2CN
(s) at 298 K.
3
NH2CN(s) + O (g) N2(g) + CO2(g) + H2O()
2 2
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CHEMISTRY FOR JEE MAIN & ADVANCED
1. An ideal gas expands in volume from 1 × 10–3 m3 to 1 × 10–2 m3 at 300 K against a constant pressure of
1 × 105 Nm–2 . The work is : [AIEEE 2004]
(A) – 900 J (B) – 900 kJ (C) 270 kJ (D) + 900 kJ
2. Consider the reaction, N2 (g) + 3H2 (g) 2NH3 (g); carried out at constant temperature and pressure. If H and
U are enthalpy change and internal energy change respectively, which of the following expressions is true ?
[AIEEE 2005]
(A) H = 0 (B) H = U (C) H < U (D) H > U
3. For a spontaneous reaction the G, equilibrium constant (K) and E°cell will be respectively [AIEEE 2005]
(A) – ve, > 1, + ve (B) + ve, > 1, – ve (C) – ve, < 1, –ve (D) – ve, > 1, – ve
4. An ideal gas is allowed to expand both reversibly and irreversibly in an isolated system. If Ti is the initial temperature
and Tf is the final temperature, which of the following statements is correct ? [AIEEE 2006]
(A) Tf > Ti for reversible process but Tf = Ti for irreversible process
(B) (Tf)rev = (Tf)irrev
(C) Tf = Ti for both reversible and irreversible processes
(D) (Tf)irrev > (Tf)rev
5. Assuming that water vapour is an ideal gas, the internal energy change (U) when 1 mol of water is vapourised at
1 bar pressure and 100°C, (Given : Molar enthalpy of vapourization of water at 1 bar and 373 K = 41 kJ mol–1 and
R = 8.3 J mol–1 K–1) will be : [AIEEE 2007]
(A) 37.904 kJ mol–1 (B) 41.00 kJ mol–1 (C) 4.100 kJ mol–1 (D) 3.7904 mol–1
8. Standard entropy of X2, Y2 and XY3 are 60, 40 and 50 JK–1 mol–1, respectively. [AIEEE 2008]
1 3
For the reaction, X + Y XY3 H = – 30 kJ. To be at equilibrium the temperature will be :
2 2 2 2
(A) 500 K (B) 750 K (C) 1000 K (D) 1250 K
9. In a fuel cell methanol is used as fuel and oxygen gas is used as an oxidizer. The reaction is
3
CH3OH() + 2 O2 (g) CO2(g) + 2H2O() [AIEEE 2009]
At 298 K, standard Gibb’s energies of formation for CH3OH(), H2O() and CO2 (g) are –166.2, –237.2 and
–394.4 kJ mol–1 respectively. If standard enthalpy of combustion of methanol is –726kJ mol–1, efficiency of the fuel
cell will be
(A) 87% (B) 90% (C) 97% (D) 80%
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THERMODYNAMICS
MOCK TEST
4. Determine which of the following reactions at constant pressure represent surrounding that do work on the system
I. 4NH3 (g) + 7O2 (g) 4NO2 (g) + 6H2O (g)
II. CO (g) + 2H2 (g) CH3OH ( )
III. C (s, graphite) + H2O (g) CO (g) + H2 (g)
IV. H2O (s) H2O ( )
(A) III, IV (B) II and III (C) II, IV (D) I and II, IV
5. A sample of liquid in a thermally insulated container (a calorimeter) is stirred for 2 hr. by a mechanical linkage to a
motor in the surrounding, for this process :
(A) w < 0; q = 0; U = 0 (B) w > 0; q > 0; U > 0 (C) w < 0; q > 0; U = 0 (D) w > 0; q = 0; U > 0
7. Which of the following reactions is associated with the most negative change in entropy ?
(A) 2SO2 (g) + O2 (g) 2SO3 (g) (B) C2H4 (g) + H2 (g) C2H6 (g)
(C) C (s, graphite) + O2 CO2(g) (D) 3C2H2 (g) C6H6 ( )
8. For the gas - phase decomposition, PCl5 (g) PCl3 (g) + Cl2 (g) :
(A) H < 0, S < 0 (B) H > 0, S > 0 (C) H > 0, S < 0 (D) H < 0, S > 0
11. The enthalpy change for a given reaction at 298 K is – x J mol–1 (x being positive). If the reaction occurs spontaneously
at 298 K, the entropy change at that temperature
(A) can be negative but numerically larger than x/298
(B) can be negative but numerically smaller than x/298
(C) cannot be negative
(D) cannot be positive
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11th Class Modules Chapter Details