Thermal Equilibrium Zero Slope and Inflection Point

𝑇𝐴 = 𝑇𝐶 = 𝑇𝐵 𝜕𝑃 𝜕2 𝑃
(𝜕𝑉) = 0 (𝜕2 𝑉) = 0
𝑇 𝑇
Ideal Gas Law
𝑃𝑉 = 𝑛𝑅𝑇 Most probable speed

Boyle’s Law (constant n, T) 2𝑅𝑇

𝑢𝑚𝑝 = √
𝑃1 𝑉1 = 𝑃2 𝑉2 𝑀
Charles’ Law (constant n, P) Average speed
𝑉1 𝑉2 8𝑅𝑇
= 𝑢 = √ 𝜋𝑀 𝑢𝑚𝑝 < 𝑢 < 𝑢𝑟𝑚𝑠
𝑇1 𝑇2
Avogadro’s Law (constant T, P) Root-mean-square speed
𝑉1 𝑉2
= 3𝑅𝑇
𝑛1 𝑛2 𝑢𝑟𝑚𝑠 = √
𝑀
Gay-Lussac’s Law (constant n, V)
𝑃1 𝑃2 Interpreting Temperature
= 𝑇 ∝ ̅̅̅̅
𝐾𝐸 =
1
𝑚𝑉 2 ̅̅̅̅
𝐾𝐸 =
3
𝑅𝑇
𝑇1 𝑇2 2 2
Molar Mass Origin of Pressure
𝑀=
𝑚
𝑀=
𝑚𝑅𝑇
=
𝜌𝑅𝑇 𝐹
𝑛 𝑃𝑉 𝑃 𝑃=
𝐴
Density Graham’s Law of Effusion
𝑃𝑀
𝜌= 𝑟𝑎𝑡𝑒1 𝑀2
𝑅𝑇
=√
𝑟𝑎𝑡𝑒2 𝑀1
Dalton’s Law (constant V, T)
𝑛1 𝑅𝑇 𝑛2 𝑅𝑇 Work
𝑃𝑇 = ∑ 𝑃𝑖 = + +⋯
𝑉 𝑉 𝑤 = 𝐹 × 𝛥𝑥 = 𝑃 × 𝛥𝑉
Partial Pressure
𝑛1 𝑃1 Potential Energy
𝑃𝑖 = 𝑥𝑖 𝑃𝑡 𝑥𝑖 = = 𝑃𝐸 = 𝑚𝑔ℎ
𝑛𝑇 𝑃𝑇
Molar Volume Kinetic Energy
𝑉 1
𝑉̅ = 𝐾𝐸 = 𝑚𝑣 2
𝑛 2
Compressibility factor Ideal gas: Z=1 Specific Heat/ Sensible Heat
𝑃𝑉̅ 𝑞 = 𝑚𝑐𝑝 𝛥𝑇
𝑍= Latent Heat
𝑅𝑇 𝑞 = 𝑚𝛥𝐻𝑡𝑟
Van der Waals EOS
𝑛𝑅𝑇 𝑛2 𝑎 𝑅𝑇 𝑎 Equation for P-V Work
𝑃= − 𝑃= ̅−𝑏
− ̅2
𝑉− 𝑛𝑏 V2 𝑉 𝑉 𝑤 = − ∫ 𝑃𝑒𝑥𝑡 𝑑𝑉
Redlich-Kwong EOS: 1st Law of Thermodynamics
𝑅𝑇 𝐴 𝛥𝑈 = 𝑞 + 𝑤
𝑃= −
𝑉̅ − 𝐵 √𝑇(𝑉̅)(𝑉̅ + 𝐵) Sign Conventions
𝛥𝑈 < 0 𝑞 < 0, Heat 𝑤 < 0, by the sys.
Virial EOS released(exo) on surr
𝐵 𝐶 𝐷 ′𝑃2
𝑍 =1+ + + +. . . = 1+𝐵𝑃+𝐶 ′
+ 𝛥𝑈 > 0 𝑞 > 0, Heat 𝑤 > 0, on the sys.
̅
𝑉 ̅2
𝑉 ̅3
𝑉 absorbed(endo) by surr
𝐷′𝑃3 +. ..
Work for reversible process
Partial Derivative
𝜕𝑧 𝑤𝑟𝑒𝑣 = − ∫ 𝑃 𝑑𝑉
( )
𝜕𝑥 𝑦 Enthalpy
Boyle Temperature
𝑎 𝐻 ≡ 𝑈 + 𝑃𝑉
𝑇𝐵 = Heat Transfer
𝑏𝑅
𝑞𝑣 = 𝛥𝑈 (𝑉 = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡) 𝑞𝑃 = 𝛥𝐻 (𝑃 = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡)
Relationship of 𝜟𝑼 and 𝜟𝑯 Isenthalpic Process (𝛥𝐻 = 0)
(assuming ideal gas) 𝛥𝑇 = 0 or 𝑇2 = 𝑇1
𝛥𝐻 = 𝛥𝑈 + 𝛥(𝑃𝑉) = 𝛥𝑈 + 𝛥𝑛𝑔𝑎𝑠 𝑅𝑇
Joule-Thomson Coefficient
(gases not involved) 𝜕𝑇
𝛥𝐻 = 𝛥𝑈 𝜇𝐽𝑇 = ( ) (for real gases, 𝑇2 ≠ 𝑇1 )
𝜕𝑃 𝐻
Calorimeter/Calorimetry (constant Pressure) 2nd Law of Thermodynamics
𝑞𝑐𝑎𝑙 + 𝑞𝑤𝑎𝑡𝑒𝑟 +. . . = −𝑞𝑟𝑥𝑛 ∆𝑆𝑢𝑛𝑖𝑣 ≥ 0
𝛥𝐻𝑟𝑥𝑛 = −𝑞𝑐𝑎𝑙 = −𝐶𝑐𝑎𝑙 𝛥𝑇 𝛥𝑆𝑢𝑛𝑖𝑣 = 𝛥𝑆𝑠𝑦𝑠 + 𝛥𝑆𝑠𝑢𝑟𝑟 ≥ 0
𝛥𝑆𝑢𝑛𝑖𝑣 > 0(𝑖𝑟𝑟𝑒𝑣𝑒𝑟𝑠𝑖𝑏𝑙𝑒)
𝛥𝑈𝑐𝑜𝑚𝑏 = 𝑛𝐶 ̅ 𝑣 ∆𝑇 𝛥𝑆𝑢𝑛𝑖𝑣 = 0 (𝑟𝑒𝑣𝑒𝑟𝑠𝑖𝑏𝑙𝑒)
𝛥𝐻𝑐𝑜𝑚𝑏 = 𝛥𝑈𝑐𝑜𝑚𝑏 + ∆𝑛𝑔 𝑅𝑇 = 𝑛𝐶 ̅ 𝑝 ∆𝑇 𝛥𝑆𝑢𝑛𝑖𝑣 < 0 (𝑛𝑜 𝑠𝑝𝑜𝑛𝑡𝑎𝑛𝑒𝑜𝑢𝑠 𝑝𝑟𝑜𝑐𝑒𝑠𝑠 𝑐𝑎𝑛 𝑜𝑐𝑐𝑢𝑟)
Hess’s Law of Heat Summation Statistical Definition of entropy
𝛥𝐻𝑟𝑥𝑛 = 𝛥𝐻1 + 𝛥𝐻2 + 𝛥𝐻3 +. .. 𝑆 = 𝑘 𝑙𝑛 𝑊
Boltzmann Constant: 𝑘 = 1.38 × 10−23 𝐽/𝐾
Standard enthalpies of Formation Entropy
𝑑𝑞
𝑜
𝛥𝐻𝑟𝑥𝑛 = ∑ 𝑛𝑖 𝛥𝐻𝑓𝑜 (𝒑𝒓𝒐𝒅𝒖𝒄𝒕𝒔) − ∑ 𝑛𝑖 𝛥𝐻𝑓𝑜 (𝒓𝒆𝒂𝒄𝒕𝒂𝒏𝒕𝒔) 𝛥𝑆 = ∫ 𝑇𝑟𝑒𝑣
𝛥𝐻
Bond enthalpies 𝛥𝑆𝑡𝑟 = 𝑇 𝑡𝑟 (latent heat)
𝑡𝑟
𝑜 𝑇2
𝛥𝐻𝑟𝑥𝑛 = ∑ 𝐵𝐸(𝒓𝒆𝒂𝒄𝒕𝒂𝒏𝒕𝒔) − ∑ 𝐵𝐸(𝒑𝒓𝒐𝒅𝒖𝒄𝒕𝒔) 𝛥𝑆 = 𝑚𝐶𝑝 𝑙𝑛 (sensible heat)
𝑇1
𝑇2 𝑉
Kirchoff’s Law 𝛥𝑆 = 𝑛𝐶𝑣 𝑙𝑛
𝑇1
+ 𝑛𝑅 𝑙𝑛 𝑉2 (ideal gas)
1
𝛥𝐻2 = 𝛥𝐻1 + 𝛥𝐶𝑝 (𝑇2 − 𝑇1 ) 𝑞𝑠𝑢𝑟𝑟
𝛥𝑆𝑠𝑢𝑟𝑟 = 𝑇
(constant temperature)
where: 𝛥𝐶𝑝 = ∑ 𝑛𝑖 𝐶𝑝𝑖 (𝒑𝒓𝒐𝒅𝒖𝒄𝒕𝒔) − 𝑛𝑖 𝐶𝑝𝑖 (𝒓𝒆𝒂𝒄𝒕𝒂𝒏𝒕𝒔) 3rd Law of Thermodynamics
𝑆 (𝑎𝑡 0𝐾) = 0
Thermodynamic processes for ideal gases
Entropy of reaction at standard conditions
𝑞 = 𝑚𝑐𝛥𝑇 = 𝐶𝛥𝑇(solids and liquids)
𝑜
𝜕𝑈 𝛥𝑆𝑟𝑥𝑛 = ∑ 𝑛𝑖 𝑆 ° (𝒑𝒓𝒐𝒅𝒖𝒄𝒕𝒔) − ∑ 𝑛𝑖 𝑆 ° (𝒓𝒆𝒂𝒄𝒕𝒂𝒏𝒕𝒔)
𝛥𝑈 = 𝑞𝑉 → 𝐶𝑉 ≡ ( ) Gibbs Free Energy
𝜕𝑇 𝑉
𝐺 ≡ 𝐻 − 𝑇𝑆 ∆𝐺 = ∆𝐻 − 𝑇∆𝑆
𝜕𝐻 ∆𝐺 < 0(𝑠𝑝𝑜𝑛𝑡𝑎𝑛𝑒𝑜𝑢𝑠); ∆𝐺 = 0(𝑟𝑒𝑣𝑒𝑟𝑠𝑖𝑏𝑙𝑒); ∆𝐺 > 0(𝑛𝑜𝑛𝑠𝑝𝑜𝑛)
𝛥𝐻 = 𝑞𝑃 → 𝐶𝑃 ≡ ( )
𝜕𝑇 𝑃 (Temperature Dependence) (Using Gibbs free Energy Formation)
° ° °
𝐶𝑝 = 𝐶𝑉 + 𝑅 ∆𝐺𝑟𝑥𝑛 = ∆𝐻𝑟𝑥𝑛 − 𝑇∆𝑆𝑟𝑥𝑛
= ∑ 𝑛𝑖 𝐺𝑓° (𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠) − ∑ 𝑛𝑖 𝐺𝑓° (𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠)
𝐶𝑉 𝐶𝑃 𝐶𝑉
𝛿=
𝐶𝑃 ∆𝐻 > 0 ∆𝐻 < 0
∆𝑆 > 0 ∆𝐺 < 0,at high temp. ∆𝐺 < 0 𝑎𝑡 𝑎𝑛𝑦 𝑡𝑒𝑚𝑝
Monatomic 3 5 5 ∆𝐺 > 0, at low temp.
𝑅 𝑅 ∆𝑆 < 0 ∆𝐺 > 0 𝑎𝑡 𝑎𝑛𝑦 𝑡𝑒𝑚𝑝 ∆𝐺 < 0,at low temp.
2 2 3
∆𝐺 > 0, at high temp.
Diatomic 5 7 7 1 N = 1 kg-m/s2
𝑅 𝑅
2 2 5 1 J = 1 N-m
1 J = 9.87x10-3 L-atm
Polyatomic 3𝑅 4𝑅 4
1 cal = 4.184 J
3
1 Pa = 1 N/m2
1 bar = 1x105 Pa = 100 kPa
Isochoric (𝛥𝑉 = 0) (Gay-Lussac’s Law) 1 atm = 1.01325x105 Pa = 101.325 Pa
𝑞 = 𝛥𝑈 = 𝑛𝐶𝑉 𝛥𝑇 𝛥𝐻 = 𝑛𝐶𝑃 𝛥𝑇 𝑤 = 0 1 atm = 1.01325 bar
𝐶𝑣 1 atm = 760 torr
𝑄= 𝑉(𝑃𝑓 − 𝑃𝑖 )
𝑅 1 atm = 101.3 J
Isobaric (𝛥𝑃 = 0) (Charles’ Law) 1mmHg = 1 torr
𝑞 = 𝛥𝐻 = 𝑛𝐶𝑃 𝛥𝑇 𝛥𝑈 = 𝑛𝐶𝑉 𝛥𝑇 𝑤 = −𝑃𝛥𝑉 1mmHg = 13.5951 g/ cm3
1 L = 1x10-3 m3
Isothermal (𝛥𝑇 = 0) (Boyle’s Law) K = °C + 273.15
𝑉 R = 0.08205 L-atm/mol-K
𝑞 = −𝑤 𝛥𝐻 = 0 𝛥𝑈 = 0 𝑤 = −𝑛𝑅𝑇 𝑙𝑛 (𝑉2 ) = 0.08314 L-bar/mol-K
1
= 1.987 cal/mol-K
Reversible Adiabatic (𝑞 = 0) = 8.314 J/ mol-K
𝑤 = 𝛥𝑈 = 𝑛𝐶𝑉 𝛥𝑇 𝛥𝐻 = 𝑛𝐶𝑃 𝛥𝑇 𝑃1 𝑉1𝛿 = 𝑃2 𝑉2𝛿 = 62.36 L-torr/mol-K
Avogadro constant (NA) NA = 6.0221367x1023 mol-1