D

THERMODYNAMICS
(1) Adiabatic process in isolated system
where dq = 0; no heat exchange.
(2) In cyclic processes all state variables
are constant. (dH; dE; dPE = 0)
(3) Intensive properties are independent
of mass; such as density, concentration.
(4) extensive properties are dependent
of mass; mass, vol, internal energy,
enthalpy, heat capacity.
(5) If x, y are extensive only if you divide
them you get something intensive.
(6) State functions only depend on initial and final state; Enthalpy, Internal Energy, Gibb’s free
energy, entropy.
(7) Path functions depend on path like work done and heat.
𝑉
(8) ∫ ⅆ𝑤 = ∫𝑉 2 𝑃 ⅆ𝑉 ; sign of work done -
1
(i) is negative if work is done by the system or expansion.
(ii) is positive if work is done on the system or compression.
(9) Heat; if heat is absorbed; q = +ve, and if heat is released; q = -ve.
1 cal = 4.18 J and 1 lit-atm = 101.3J = 24.2 cal.
(10) ZEROTH LAW; if A and B in thermal equilibrium and A and C are in thermal equilibrium
then B and C are also is thermal equilibrium such that A, B and C are in a system.
(11) FIRST LAW; Energy is neither created not destroyed; 𝛥𝑢 = 𝑞 + 𝑤
(12) If process is isothermal E = 0, so q + w = 0
(13) If process is adiabatic, q = 0, so w = 𝛥𝑢.
(14) if process is isochoric, w = 0, so q = 𝛥𝑢
(15) if process is isobaric, 𝛥𝑃 = 0, so q which is called enthalpy in this case is;
𝛥𝐻 = 𝛥𝑢 + 𝛥(𝑛𝑔 𝑅𝑇) where ng is change in moles of gas.
ⅆ𝑞
(16) Heat Capacity (C); 𝐶 = (Amount of heat req to raise temp of system by 1C)
ⅆ𝑇
(17) at constant volume; Cv is heat capacity. ∫ ⅆ𝑈 = ∫ 𝑛𝐶𝑣 ⅆ𝑇
(18) at constant pressure; Cp is heat capacity. ∫ ⅆ𝐻 = ∫ 𝑛𝐶𝑃 ⅆ𝑇
(19) Specific heat capacity; heat required to raise T by 1C of 1g; (Cs)
𝐶
𝐶𝑠 = and ∫ ⅆ𝑞 = ∫ 𝑚𝐶 ⅆ𝑇.
𝑚
𝐶𝑝
(20) Cp – Cv = R and = 𝛾 (poison’s ratio)
𝐶𝑣
(21) Reversible isothermal processes;
When Pexternal and Pgas difference is infinitely small.
𝑣2 𝑣2 𝑃1
𝑤 = −2.303𝑛𝑅𝑇 𝑙𝑜𝑔 where =
𝑣1 𝑣1 𝑃2
(22) Reversible adiabatic processes;
1−𝛾
𝑃 ⋅ 𝑣 𝛾 = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡; 𝑇 ⋅ 𝑣 𝛾−1 = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡; 𝑇 ⋅ 𝑃 𝛾 = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡
For work done;
𝑃2 𝑣2 − 𝑃1 𝑣1 𝑅𝛥𝑇
𝑤 = 𝑛𝐶𝑣 𝛥𝑇 = =
𝛾−1 𝛾−1
ⅆ𝑃 −𝑝 ⅆ𝑃 𝑃
(23) For isothermal process; = ; For adiabatic process; = −𝛾( )
ⅆ𝑣 𝑣 ⅆ𝑣 𝑉
(24) From same state to same final pressure,
For expansion; |𝑤𝑟𝑒𝑣;𝑖𝑠𝑜𝑡ℎ𝑒𝑟𝑚𝑎𝑙 | > |𝑤𝑟𝑒𝑣;𝑎ⅆ𝑖𝑎𝑏𝑎𝑡𝑖𝑐 |, for contraction opposite.
(25) Irreversible adiabatic;
𝑇 𝑇
𝐶𝑣 𝛥𝑇 = −𝑃𝑒𝑥𝑡 𝑅 [ 2 − 1 ] and area under P-V curve gives work done.
𝑃2 𝑃1
(26) Let w1, w2, w3, w4 be works done in isothermal, adiabatic, isobaric and isochoric
processes. In expansions; w3 > w1 > w2 > w4. And w3 > w2 > w1 > w4 for compression.
(27) Water expands when it freezes. If temperature increases, 𝛥𝐻 𝑖𝑠 𝑝𝑜𝑠𝑖𝑡𝑖𝑣𝑒.
𝑣
(28) In graphs, work done can be represented by 𝑃1 𝑣1 𝑙𝑛 ( 2).
𝑣1
(29) If the expansion is carried out freely it is simultaneously both isothermal and adiabatic.
(30) Internal energy is directly proportional to atomicity.
(31) If ∆𝑛 = +𝑣𝑒 𝑡ℎ𝑒𝑛 ∆𝑠 𝑎𝑙𝑠𝑜 + 𝑣𝑒, 𝑠𝑎𝑚𝑒 𝑓𝑜𝑟 − 𝑣𝑒.
(32) Exothermic processes are always spontaneous. Entropy of gases is highest.
(33) Change in entropy is highest at equilibrium.
𝑞
(34) 𝛥𝑠 = 𝑟𝑒𝑣 and for equilibrium, 𝛥𝑠 of universe = 0.
𝑇
𝑇1− 𝑇2
(35) For irreversible process 𝛥𝑠 = 𝑞 [ ] where T1 > T2
𝑇1 𝑇2
All naturally occurring irreversible processes are spontaneous.
(36) ENTROPY CHANGE IN REVERSIBLE PROCESS
𝑇2 𝑣2 𝑇2 𝑃1
𝛥𝑠 = 𝐶𝑣 𝑙𝑛 ( ) + 𝑅 𝑙𝑛 ( ) = 𝐶𝑃 ln ( ) + 𝑅 ln ( )
𝑇1 𝑣1 𝑇1 𝑃2
This is for one mole of ideal gas.
𝑣
For (i) Isothermal; 𝛥𝑠 = 𝑛𝑅 𝑙𝑛 ( 2)
𝑣1
𝑇2
(ii) Isochoric; 𝑛𝐶𝑣 𝑙𝑛 ( ) = 𝛥𝑆
𝑇1
𝑇
(iii) Isobaric; 𝛥𝑠 = 𝑛𝑐𝑝 𝑙𝑛 ( 2 )
𝑇1
𝛥𝐻
(iv) Phase transition at equilibrium; ∆𝑠 = for vaporisation, fusion etc…
𝑇
(37) Gibb’s Free Energy; Non P-V work done in the system; useful work.
𝛥𝐺 = 𝛥𝐻 − 𝑇𝛥𝑠 and 𝛥𝐺𝑠𝑦𝑠 = −𝑇𝛥𝑆
State function; extensive property. If 𝛥𝐺 = −𝑣𝑒 𝑡ℎ𝑒𝑛 𝑠𝑝𝑜𝑛𝑡𝑎𝑛𝑒𝑜𝑢𝑠, +𝑣𝑒 𝑖𝑠 𝑛𝑜𝑛 −
𝑠𝑝𝑜𝑛𝑡𝑎𝑛𝑒𝑜𝑢𝑠 𝑎𝑛ⅆ 0 𝑖𝑠 𝑒𝑞𝑢𝑖𝑙𝑖𝑏𝑟𝑖𝑢𝑚.
(38) Cases of spontaneity;
(i) When ΔH -ve and ΔS +ve, then ΔG is always -ve, spontaneous
(ii) When ΔH +ve, and ΔS +ve, then spontaneous only at high temperatures.
(iii) ΔH -ve and ΔS -ve, then spontaneous only at low temperatures.
(iv) ΔH +ve and ΔS -ve, always non spontaneous.
(39) JEE ADVANCED TOPICS FROM THERMODYNAMICS;
𝑃
(i) Gibb’s Helmholtz equation; If K is equilibrium constant which is 𝑅
𝑃𝑝
0
then at equilibrium; 𝛥𝐺 = −𝑛𝑅𝑇 𝑙𝑛(𝐾). And at standard state K = 1.
(ii) If Cv or Cp are dependent on temperature.
𝑛𝑏𝑇 2 𝑛𝑐𝑇 3
𝛥𝑢 = 𝑛𝑎𝑇 + +
2 3
(iii) Kirchoff’s Law; 𝛥𝑟 𝐶𝑃 is independent of temperature then
𝛥𝐻2 − 𝛥𝐻1 = 𝛥𝑟 𝐶𝑃 (𝑇2 − 𝑇1 )
(iv) Expression for Gibb’s free energy; 𝛥𝐺 = 𝑉 ⅆ𝑃 − 𝑆 ⅆ𝑇
𝑃
(v) But at constant temperature; 𝛥𝐺 = 𝑛𝑅𝑇 𝑙𝑛 ( 2 )
𝑃1
(vi) Third Law; Entropy of pure perfect crystalline substances at 0K is 0. For a solid X,
𝑇23 − 𝑇13
𝛥5 = 𝑎 [ ]
3
(vii) When temperature independent or ΔrCp = 0, then ΔHT1 = ΔHT2 and same goes for ΔS.
(viii) Carnot engine; Engine efficiency is a theoretical concept;
𝑄1 +𝑄2 𝑇2
=1− = 𝜂
𝑄1 𝑇1
(ix) Clausius inequality;
ⅆ𝑄𝑟𝑒𝑣 ⅆ𝑄(𝑖𝑟𝑟𝑒𝑣)
∮ = 0 and ∮ ⅆ𝑠 = 0; ∮ < 0 𝑎𝑛ⅆ ∮ ⅆ𝑠(𝑖𝑟𝑟𝑒𝑣) < 0
𝑇 𝑇
For a closed system with P-V work only;
ⅆ𝑊 (𝑟𝑒𝑣 )
∮ 𝑃ⅆ𝑉 + 𝑉ⅆ𝑃 = 0; ∮ = 0 𝑎𝑛ⅆ ∮ 𝑃ⅆ𝑉 ≠ 0
𝑃
(x) In melting one mole of ice at 10C into water, ΔSuniverse increases, and same with freezing one
mole of water to ice at -10C.
(xi) When a real gas is subjected to adiabatic compression it gets cooled.
(xii) When graph (other than P-V) given and P is not constant, find equation of line and
substitute in W = PextdV
𝑛1 𝐶𝑚 ,+𝑛2 𝐶𝑚2
(x) Average Cv or Cp =
𝑛1 +𝑛2
(xi) For ΔH of a mixture; 𝛥𝐻 = [𝑛1 𝐶𝑃𝑚 + 𝑛2 𝐶𝑝𝑚 ]𝛥𝑇
𝑇 +𝑇
(xii) For questions involving thermal equilibrium, 𝑇𝑓 = 1 2 and for Entropy change;
2
𝑇𝑓 𝑇𝑓
𝛥𝑠 = 𝑛𝐶𝑃 𝑙𝑛 ( ) + 𝑛𝐶𝑝 𝑙𝑛 ( )
𝑇1 𝑇2
(xiii)