
Introduce chemical thermodynamics by examining energy exchange between a system and its surroundings. Explore types of systems and processes, the first law, and Gibbs free energy in macroscopic terms.
Explore how the system, surroundings, and boundary define the universe in thermodynamics, using a cup of tea analogy to show how a boundary separates system from surroundings.
Explore open, closed, and isolated systems and how matter and energy exchange with the surroundings. Learn how each type limits or enables these exchanges in thermodynamics.
Explore exothermic reactions, where heat evolves during processes like nuclear fission or fusion, combustion of fuels, and phase changes such as condensation and freezing.
Explore endothermic reactions that absorb heat, from photosynthesis driven by light energy to evaporation and sublimation, including methane cracking into carbon and hydrogen.
Examine six thermodynamic process types, such as isothermal, adiabatic, isobaric, and isochoric, and see how temperature, pressure, and volume constraints govern energy transfer.
Internal energy is a state function equal to the sum of kinetic and potential energies, including vibrational, rotational, and translational energies, and depends only on the initial and final states.
Classify thermodynamic properties as extensive or intensive by whether their values depend on the amount of matter; volume and pressure are extensive, while temperature is intensive.
Examine how state functions depend on initial and final states, with volume and entropy as examples, while pressure remains not a state function and instantaneous values are not measurable.
Explains mechanical work as pressure-volume work, with a piston moving when internal gas pressure exceeds external pressure. Shows the work expression W = -P_ext ΔV for expansion.
Understand maximum work (Wmax) for a reversible, isothermal ideal-gas process, derived by summing infinitesimal dW and noting work is path-dependent.
Explore the second law of thermodynamics, detailing heat flow from higher to lower temperatures and the permanent energy changes between a system and its surroundings during work.
Enthalpy is the total heat content of a system, defined as H = U + PV, a state function whose change at constant pressure is ΔH = ΔU + PΔV.
Explore the relationship between ΔH and ΔU for gas-phase reactions, showing that ΔH = ΔU + Δ(n_gas) RT under ideal gas assumptions.
Hess's law shows that the enthalpy change of a reaction equals the sum of enthalpy changes for any path, independent of steps, including standard enthalpy of formation, atomization, or neutralization.
Apply thermochemical equations to relate reactants and products in standard states to delta H, carbon and hydrogen form methane, and follow rules to add, multiply, or reverse equations with sign.
Explore standard enthalpy changes and major enthalpy types—formation, atomization, combustion, vaporization, fusion, sublimation—under standard states (298 K, 1 bar) in chemical thermodynamics.
Explain bond energy and bond enthalpies as energy required or released during bond formation or breaking, and define bond dissociation enthalpy, atomization energy, and mean bond enthalpy for polyatomic molecules.
Calculate the lattice energy of NaCl using the Born-Haber cycle by summing sodium sublimation, ionization, chlorine atom formation from Cl2, chlorine electron affinity, and dissolution contributions.
Explore spontaneous processes, where sublimation and vaporization occur without added energy, illustrated by solid to gas and liquid to gas transitions, governed by Gibbs free energy and related factors.
Use Gibbs free energy, G = H − T S, to predict spontaneity: ΔG < 0 spontaneous, ΔG > 0 non spontaneous, or ΔG = 0 at equilibrium.
Explore standard Gibbs free energy change under standard-state conditions and link to quotient Q, equilibrium constant K, and the relation Delta G equals Delta G standard plus RT ln Q.
Explore entropy, the randomness of a system, and how solid–liquid–gas transitions (fusion, vaporization, sublimation, condensation) increase entropy, while gas–liquid and liquid–solid transitions decrease it.
Explore entropy changes during phase transitions—fusion, vaporization, sublimation, condensation, and freezing—by analyzing heat input and the sign of ΔS and its relation to ΔG.
Heat capacity is the heat required to raise a system's temperature by one degree, Q = C ΔT; specific heat capacity depends on mass, describing heat per unit mass.
Explore the relation between Cp and Cv, derive Cp minus Cv equals R for an ideal gas, and show Cp is always greater than Cv.
Define the third law of thermodynamics: the entropy of a pure crystalline substance becomes zero at absolute zero, zero kelvin. Reduce temperature and randomness vanishes, yielding zero entropy.
Examine entropy changes during phase transitions (fusion, vaporization, sublimation) and for ideal gases, with two forms: ΔS = Cp ln(T2/T1) for isobaric and ΔS = Cv ln(T2/T1) for isochoric processes.
Apply Hess's law to determine enthalpy of formation, reaction enthalpies, and transformation enthalpies between forms. Use bond energies and resonance energy to quantify overall enthalpy changes.
Explore Gibbs free energy as the criterion for spontaneity, using delta G equals delta H minus T delta S to predict when a process is spontaneous at different temperatures.
Apply the first law of thermodynamics, ΔU = Q + W (heat and work), to a chemical thermodynamics problem, showing that the change in internal energy is positive in kilojoules.
Compute the isothermal work for one mole expanding from 25 to 250 liters at 1 atm and 300 K using W = -nRT ln(V2/V1), yielding about -5.7 kJ.
Compute the change in internal energy at 298 kelvin for a reaction by applying Delta U equals Delta H minus Delta n_g R T, counting gaseous products and reactants.
Compute the entropy change for water vaporization at 100 degrees Celsius using ΔS = ΔH_vap / T, with ΔH_vap = 40.8 kJ and T = 373.15 K, giving 109 J/K.
Analyze ice in equilibrium with water at 0 °C (273.15 kelvin) and convert temperatures to perform the thermodynamic calculation. Conclude that the result is zero, indicating thermodynamic equilibrium.
Tackle level-2 numerical problems in chemical thermodynamics, computing reaction enthalpies from formation data, evaluating spontaneity with delta G, and predicting equilibrium constants from Gibbs free energy.
Solve bond enthalpy calculations, resonance energy, Carnot efficiency, and combustion and formation enthalpies, including reversible compression of an ideal gas.
SUMMARY
Thermodynamics deals with energy changes in chemical or physical processes and enables us to study these changes quantitatively and to make useful predictions. For these purposes, we divide the universe into the system and the surroundings. Chemical or physical processes lead to evolution or absorption of heat (q), part of which may be converted into work (w). These quantities are related through the first law of thermodynamics via ∆U = q + w. ∆U, change in internal energy, depends on initial and final states only and is a state function, whereas q and w depend on the path and are not the state functions. We follow sign conventions of q and w by giving the positive sign to these quantities when these are added to the system. We can measure the transfer of heat from one system to another which causes the change in temperature. The magnitude of rise in temperature depends on the heat capacity (C) of a substance. Therefore, heat absorbed or evolved is q = C∆T. Work can be measured by w = –pex ∆V, in case of expansion of gases. Under reversible process, we can put pex = p for infinitesimal changes in the volume making wrev = – p dV. In this condition, we can use gas equation, pV = nRT.
At constant volume, w = 0, then ∆U = qV , heat transfer at constant volume. But in study of chemical reactions, we usually have constant pressure. We define another state function enthalpy. Enthalpy change, ∆H = ∆U + ∆ngRT, can be found directly from the heat changes at constant pressure, ∆H = qp .
There are varieties of enthalpy changes. Changes of phase such as melting, vaporization and sublimation usually occur at constant temperature and can be characterized by enthalpy changes which are always positive. Enthalpy of formation, combustion and other enthalpy changes can be calculated using Hess’s law.
First law of thermodynamics does not guide us about the direction of chemical reactions i.e., what is the driving force of a chemical reaction. For isolated systems, ∆U = 0. We define another state function, S, entropy for this purpose. Entropy is a measure of disorder or randomness. For a spontaneous change, total entropy change is positive. Therefore, for an isolated system, ∆U = 0, ∆S > 0, so entropy change distinguishes a spontaneous change, while energy change does not. Entropy changes can be measured by the equation ∆S = qrev/T for a reversible process. qrev/T is independent of path.
1 Choose the correct answer. A thermodynamic state function is a quantity (i) used to determine heat changes (ii) whose value is independent of path (iii) used to determine pressure volume work (iv) whose value depends on temperature only.
2 For the process to occur under adiabatic conditions, the correct condition is: (i) ∆T = 0 (ii) ∆p = 0 (iii) q = 0 (iv) w = 0
3 The enthalpies of all elements in their standard states are: (i) unity (ii) zero (iii) < 0 (iv) different for each element
4 The enthalpy of combustion of methane, graphite and dihydrogen at 298 K are, –890.3 kJ mol–1 –393.5 kJ mol–1, and –285.8 kJ mol–1 respectively. Enthalpy of formation of CH4 (g) will be
(i) –74.8 kJ mol–1 (ii) –52.27 kJ mol–1 (iii) +74.8 kJ mol–1 (iv) +52.26 kJ mol–1 .
5 A reaction, A + B → C + D + q is found to have a positive entropy change. The reaction will be (i) possible at high temperature (ii) possible only at low temperature (iii) not possible at any temperature (v) possible at any temperature
6 In a process, 701 J of heat is absorbed by a system and 394 J of work is done by the system. What is the change in internal energy for the process?
7 Calculate the number of kJ of heat necessary to raise the temperature of 60.0 g of aluminium from 35°C to 55°C. Molar heat capacity of Al is 24 J mol–1 K–1 .
8 Enthalpy of combustion of carbon to CO2 is –393.5 kJ mol–1. Calculate the heat released upon formation of 35.2 g of CO2 from carbon and dioxygen gas.
9 Enthalpies of formation of CO(g), CO2 (g), N2O(g) and N2O4 (g) are –110, – 393, 81 and 9.7 kJ mol–1 respectively. Find the value of ∆rH for the reaction: N2O4 (g) + 3CO(g) → N2O(g) + 3CO2 (g)
10 For an isolated system, ∆U = 0, what will be ∆S ?
11 For the reaction at 298 K, 2A + B → C ∆H = 400 kJ mol–1 and ∆S = 0.2 kJ K–1 mol–1 At what temperature will the reaction become spontaneous considering ∆H and ∆S to be constant over the temperature range.
12 For the reaction, 2 Cl(g) → Cl2 (g), what are the signs of ∆H and ∆S ?