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Unit 6: Thermodynamics

Thermodynamic terms.

  • System and Surroundings (Opens a modal)
  • State and Path functions (Opens a modal)
  • Thermodynamic terms Get 3 of 4 questions to level up!

First law of thermodynamics

  • First Law of Thermodynamics introduction (Opens a modal)
  • More on internal energy (Opens a modal)
  • Calculating internal energy and work example (Opens a modal)
  • Heat and temperature (Opens a modal)
  • First law of thermodynamics Get 3 of 4 questions to level up!

Applications of first law of thermodynamics

  • Pressure-volume work (Opens a modal)
  • Macrostates and microstates (Opens a modal)
  • Quasistatic and reversible processes (Opens a modal)
  • Work from expansion (Opens a modal)
  • PV-diagrams and expansion work (Opens a modal)
  • Calculating work done. Get 3 of 4 questions to level up!

Measurement of U and H- Calorimetry

  • Enthalpy (Opens a modal)
  • Specific heat and latent heat of fusion and vaporization (Opens a modal)
  • Heat capacity (Opens a modal)
  • Worked example: Measuring the energy content of foods using soda-can calorimetry (Opens a modal)
  • Constant-pressure calorimetry (Opens a modal)
  • Heat capacity and calorimetry Get 3 of 4 questions to level up!

Enthalpy change

  • Endothermic and exothermic processes (Opens a modal)
  • Representing endothermic and exothermic processes using energy diagrams (Opens a modal)
  • Enthalpy of reaction (Opens a modal)
  • Worked example: Measuring enthalpy of reaction using coffee-cup calorimetry (Opens a modal)
  • Introduction to enthalpy of reaction Get 3 of 4 questions to level up!

Hess's law

  • Hess's law (Opens a modal)
  • Worked example: Using Hess's law to calculate enthalpy of reaction (Opens a modal)
  • Hess's law Get 3 of 4 questions to level up!

Enthalpy changes during phase transformations

  • Enthalpy and phase changes (Opens a modal)
  • Heating curve for water (Opens a modal)

Enthalpy of formation

  • Enthalpy of formation (Opens a modal)
  • Enthalpy of formation Get 3 of 4 questions to level up!

Bond enthalpies

  • Bond enthalpies (Opens a modal)
  • Worked example: Using bond enthalpies to calculate enthalpy of reaction (Opens a modal)
  • Bond enthalpies Get 3 of 4 questions to level up!

Enthalpy changes for other processes

  • Standard enthalpy change for combustion (Opens a modal)
  • Standard enthalpy of atomisation (Opens a modal)
  • Standard enthalpy changes for combustion and atomisation Get 3 of 4 questions to level up!

Calculating enthalpy changes for various processes

  • Worked example: Calculating the enthalpy change for a reaction. (Opens a modal)
  • Calculating enthalpy changes for various processes Get 3 of 4 questions to level up!

Spontaneity

  • Introduction to entropy (Opens a modal)
  • Second Law of Thermodynamics (Opens a modal)
  • Work done by isothermic process (Opens a modal)
  • Reconciling thermodynamic and state definitions of entropy (Opens a modal)
  • Entropy intuition (Opens a modal)
  • More on entropy (Opens a modal)
  • Entropy changes! Get 3 of 4 questions to level up!

Thermodynamics Problem Solving in Physical Chemistry

Study guide and map, by kathleen e. murphy.

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5.E: Chemical Thermodynamics (Practice Problems with Answers)

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These are homework exercises to accompany the Textmap created for "Chemistry: The Central Science" by Brown et al. Complementary General Chemistry question banks can be found for other Textmaps and can be accessed here . In addition to these publicly available questions, access to private problems bank for use in exams and homework is available to faculty only on an individual basis; please contact Delmar Larsen for an account with access permission.

19.1: Spontaneous Processes

19.2: entropy and the second law of thermodynamics, conceptual problems.

  • A Russian space vehicle developed a leak, which resulted in an internal pressure drop from 1 atm to 0.85 atm. Is this an example of a reversible expansion? Has work been done?
  • Which member of each pair do you expect to have a higher entropy? Why?
  • solid phenol or liquid phenol
  • 1-butanol or butane
  • cyclohexane or cyclohexanol
  • 1 mol of N 2 mixed with 2 mol of O 2 or 2 mol of NO 2
  • 1 mol of O 2 or 1 mol of O 3
  • 1 mol of propane at 1 atm or 1 mol of propane at 2 atm
  • Determine whether each process is reversible or irreversible.
  • ice melting at 0°C
  • salt crystallizing from a saline solution
  • evaporation of a liquid in equilibrium with its vapor in a sealed flask
  • a neutralization reaction
  • cooking spaghetti
  • the reaction between sodium metal and water
  • oxygen uptake by hemoglobin
  • evaporation of water at its boiling point
  • Explain why increasing the temperature of a gas increases its entropy. What effect does this have on the internal energy of the gas?
  • For a series of related compounds, does ΔS vap increase or decrease with an increase in the strength of intermolecular interactions in the liquid state? Why?
  • Is the change in the enthalpy of reaction or the change in entropy of reaction more sensitive to changes in temperature? Explain your reasoning.
  • Solid potassium chloride has a highly ordered lattice structure. Do you expect ΔS soln to be greater or less than zero? Why? What opposing factors must be considered in making your prediction?
  • Aniline (C 6 H 5 NH 2 ) is an oily liquid at 25°C that darkens on exposure to air and light. It is used in dying fabrics and in staining wood black. One gram of aniline dissolves in 28.6 mL of water, but aniline is completely miscible with ethanol. Do you expect ΔS soln in H 2 O to be greater than, less than, or equal to ΔS soln in CH 3 CH 2 OH? Why?

Conceptual Answers

  • No, it is irreversible; no work is done because the external pressure is effectively zero.
  • irreversible
  • Water has a highly ordered, hydrogen-bonded structure that must reorganize to accommodate hydrophobic solutes like aniline. In contrast, we expect that aniline will be able to disperse randomly throughout ethanol, which has a significantly less ordered structure. We therefore predict that ΔS soln in ethanol will be more positive than ΔS soln in water.

Numerical Problems

  • Liquid nitrogen, which has a boiling point of −195.79°C, is used as a coolant and as a preservative for biological tissues. Is the entropy of nitrogen higher or lower at −200°C than at −190°C? Explain your answer. Liquid nitrogen freezes to a white solid at −210.00°C, with an enthalpy of fusion of 0.71 kJ/mol. What is its entropy of fusion? Is freezing biological tissue in liquid nitrogen an example of a reversible process or an irreversible process?
  • Using the second law of thermodynamics, explain why heat flows from a hot body to a cold body but not from a cold body to a hot body.
  • One test of the spontaneity of a reaction is whether the entropy of the universe increases: ΔS univ > 0. Using an entropic argument, show that the following reaction is spontaneous at 25°C:

4Fe(s) + 3O 2 (g) → 2Fe 2 O 3 (s)

Why does the entropy of the universe increase in this reaction even though gaseous molecules, which have a high entropy, are consumed?

  • Calculate the missing data in the following table.

Based on this table, can you conclude that entropy is related to the nature of functional groups? Explain your reasoning.

The text states that the magnitude of ΔS vap tends to be similar for a wide variety of compounds. Based on the values in the table, do you agree?

19.3: The Molecular Interpretation of Entropy

19.4: entropy changes in chemical reactions, 19.5: gibbs free energy.

  • How does each example illustrate the fact that no process is 100% efficient?
  • burning a log to stay warm
  • the respiration of glucose to provide energy
  • burning a candle to provide light
  • Neither the change in enthalpy nor the change in entropy is, by itself, sufficient to determine whether a reaction will occur spontaneously. Why?
  • If a system is at equilibrium, what must be the relationship between ΔH and ΔS?
  • The equilibrium 2AB⇌A 2 B 2 is exothermic in the forward direction. Which has the higher entropy—the products or the reactants? Why? Which is favored at high temperatures?
  • Is ΔG a state function that describes a system or its surroundings? Do its components—ΔH and ΔS—describe a system or its surroundings?
  • How can you use ΔG to determine the temperature of a phase transition, such as the boiling point of a liquid or the melting point of a solid?
  • Occasionally, an inventor claims to have invented a “perpetual motion” machine, which requires no additional input of energy once the machine has been put into motion. Using your knowledge of thermodynamics, how would you respond to such a claim? Justify your arguments.
  • Must the entropy of the universe increase in a spontaneous process? If not, why is no process 100% efficient?
  • The reaction of methyl chloride with water produces methanol and hydrogen chloride gas at room temperature, despite the fact that ΔH ∘ rxn = 7.3 kcal/mol. Using thermodynamic arguments, propose an explanation as to why methanol forms.
  • In order for the reaction to occur spontaneously, ΔG for the reaction must be less than zero. In this case, ΔS must be positive, and the TΔS term outweighs the positive value of ΔH.
  • Use the tables in the text to determine whether each reaction is spontaneous under standard conditions. If a reaction is not spontaneous, write the corresponding spontaneous reaction.
  • \(\mathrm{H_2(g)}+\frac{1}{2}\mathrm{O_2(g)}\rightarrow\mathrm{H_2O(l)}\)
  • 2H 2 (g) + C 2 H 2 (g) → C 2 H 6 (g)
  • (CH 3 ) 2 O(g) + H 2 O(g) → 2CH 3 OH(l)
  • CH 4 (g) + H 2 O(g) → CO(g) + 3H 2 (g)
  • K 2 O 2 (s) → 2K(s) + O 2 (g)
  • PbCO 3 (s) → PbO(s) + CO 2 (g)
  • P 4 (s) + 6H 2 (g) → 4PH 3 (g)
  • 2AgCl(s) + H 2 S(g) → Ag 2 S(s) + 2HCl(g)
  • Nitrogen fixation is the process by which nitrogen in the atmosphere is reduced to NH 3 for use by organisms. Several reactions are associated with this process; three are listed in the following table. Which of these are spontaneous at 25°C? If a reaction is not spontaneous, at what temperature does it become spontaneous?
  • A student was asked to propose three reactions for the oxidation of carbon or a carbon compound to CO or CO 2 . The reactions are listed in the following table. Are any of these reactions spontaneous at 25°C? If a reaction does not occur spontaneously at 25°C, at what temperature does it become spontaneous?
  • Tungsten trioxide (WO 3 ) is a dense yellow powder that, because of its bright color, is used as a pigment in oil paints and water colors (although cadmium yellow is more commonly used in artists’ paints). Tungsten metal can be isolated by the reaction of WO 3 with H 2 at 1100°C according to the equation WO 3 (s) + 3H 2 (g) → W(s) + 3H 2 O(g). What is the lowest temperature at which the reaction occurs spontaneously? ΔH° = 27.4 kJ/mol and ΔS° = 29.8 J/K.
  • Sulfur trioxide (SO 3 ) is produced in large quantities in the industrial synthesis of sulfuric acid. Sulfur dioxide is converted to sulfur trioxide by reaction with oxygen gas.
  • Write a balanced chemical equation for the reaction of SO 2 with O 2 (g) and determine its ΔG°.
  • What is the value of the equilibrium constant at 600°C?
  • If you had to rely on the equilibrium concentrations alone, would you obtain a higher yield of product at 400°C or at 600°C?
  • Calculate ΔG° for the general reaction MCO 3 (s) → MO(s) + CO 2 (g) at 25°C, where M is Mg or Ba. At what temperature does each of these reactions become spontaneous?
  • The reaction of aqueous solutions of barium nitrate with sodium iodide is described by the following equation:

Ba(NO 3 ) 2 (aq) + 2NaI(aq) → BaI 2 (aq) + 2NaNO 3 (aq)

You want to determine the absolute entropy of BaI 2 , but that information is not listed in your tables. However, you have been able to obtain the following information:

You know that ΔG° for the reaction at 25°C is 22.64 kJ/mol. What is ΔH° for this reaction? What is S° for BaI 2 ?

Numerical Answers

  • −237.1 kJ/mol; spontaneous as written
  • −241.9 kJ/mol; spontaneous as written
  • 8.0 kJ/mol; spontaneous in reverse direction.
  • 141.9 kJ/mol; spontaneous in reverse direction.
  • Not spontaneous at any T
  • Not spontaneous at 25°C; spontaneous above 7400 K
  • Spontaneous at 25°C
  • MgCO 3 : ΔG° = 63 kJ/mol, spontaneous above 663 K; BaCO 3 : ΔG° = 220 kJ/mol, spontaneous above 1562 K

19.6: Free Energy and Temperature

19.7: free energy and the equilibrium constant.

  • Do you expect products or reactants to dominate at equilibrium in a reaction for which ΔG° is equal to
  • 1.4 kJ/mol?
  • 105 kJ/mol?
  • −34 kJ/mol?
  • The change in free energy enables us to determine whether a reaction will proceed spontaneously. How is this related to the extent to which a reaction proceeds?
  • What happens to the change in free energy of the reaction N 2 (g) + 3F 2 (g) → 2NF 3 (g) if the pressure is increased while the temperature remains constant? if the temperature is increased at constant pressure? Why are these effects not so important for reactions that involve liquids and solids?
  • Compare the expressions for the relationship between the change in free energy of a reaction and its equilibrium constant where the reactants are gases versus liquids. What are the differences between these expressions?
  • Carbon monoxide, a toxic product from the incomplete combustion of fossil fuels, reacts with water to form CO 2 and H 2 , as shown in the equation CO(g)+H 2 O(g)⇌CO 2 (g)+H 2 (g), for which ΔH° = −41.0 kJ/mol and ΔS° = −42.3 J cal/(mol·K) at 25°C and 1 atm.
  • What is ΔG° for this reaction?
  • What is ΔG if the gases have the following partial pressures: P CO = 1.3 atm, \(P_{\mathrm{H_2O}}\) = 0.8 atm, \(P_{\mathrm{CO_2}}\) = 2.0 atm, and \(P_{\mathrm{H_2}}\) = 1.3 atm?
  • What is ΔG if the temperature is increased to 150°C assuming no change in pressure?
  • Methane and water react to form carbon monoxide and hydrogen according to the equation CH 4 (g) + H 2 O(g) ⇌ CO(g) + 3H 2 (g).
  • What is the standard free energy change for this reaction?
  • What is K p for this reaction?
  • What is the carbon monoxide pressure if 1.3 atm of methane reacts with 0.8 atm of water, producing 1.8 atm of hydrogen gas?
  • What is the hydrogen gas pressure if 2.0 atm of methane is allowed to react with 1.1 atm of water?
  • At what temperature does the reaction become spontaneous?
  • Calculate the equilibrium constant at 25°C for each equilibrium reaction and comment on the extent of the reaction.
  • CCl 4 (g)+6H 2 O(l)⇌CO 2 (g)+4HCl(aq); ΔG° = −377 kJ/mol
  • Xe(g)+2F 2 (g)⇌XeF 4 (s); ΔH° = −66.3 kJ/mol, ΔS° = −102.3 J/(mol·K)
  • PCl 3 (g)+S⇌PSCl 3 (l); ΔG ∘ f (PCl 3 ) = −272.4 kJ/mol, ΔG ∘ f (PSCl 3 ) = −363.2 kJ/mol
  • 2KClO 3 (s)⇌2KCl(s)+3O 2 (g); ΔG° = −225.8 kJ/mol
  • CoCl 2 (s)+6H 2 O(g)⇌CoCl 2 ⋅6H 2 O(s); ΔH ∘ rxn = −352 kJ/mol, ΔS ∘ rxn = −899 J/(mol·K)
  • 2PCl 3 (g)+O 2 (g)⇌2POCl 3 (g); ΔG ∘ f (PCl 3 ) = −272.4 kJ/mol, ΔG ∘ f (POCl 3 ) = −558.5 kJ/mol
  • The gas-phase decomposition of N 2 O 4 to NO 2 is an equilibrium reaction with K p = 4.66 × 10 −3 . Calculate the standard free-energy change for the equilibrium reaction between N 2 O 4 and NO 2 .
  • The standard free-energy change for the dissolution K 4 Fe(CN) 6 ⋅H 2 O(s)⇌4K + (aq)+Fe(CN) 6 4− (aq)+H 2 O(l) is 26.1 kJ/mol. What is the equilibrium constant for this process at 25°C?
  • Ammonia reacts with water in liquid ammonia solution (am) according to the equation NH 3 (g) + H 2 O(am) ⇌ NH 4 + (am) + OH − (am). The change in enthalpy for this reaction is 21 kJ/mol, and ΔS° = −303 J/(mol·K). What is the equilibrium constant for the reaction at the boiling point of liquid ammonia (−31°C)?
  • At 25°C, a saturated solution of barium carbonate is found to have a concentration of [Ba 2 + ] = [CO 3 2− ] = 5.08 × 10 −5 M. Determine ΔG° for the dissolution of BaCO 3 .
  • Lead phosphates are believed to play a major role in controlling the overall solubility of lead in acidic soils. One of the dissolution reactions is Pb 3 (PO 4 ) 2 (s)+4H + (aq)⇌3Pb 2 + (aq)+2H 2 PO 4 − (aq), for which log K = −1.80. What is ΔG° for this reaction?
  • The conversion of butane to 2-methylpropane is an equilibrium process with ΔH° = −2.05 kcal/mol and ΔG° = −0.89 kcal/mol.
  • What is the change in entropy for this conversion?
  • Based on structural arguments, are the sign and magnitude of the entropy change what you would expect? Why?
  • What is the equilibrium constant for this reaction?
  • The reaction of CaCO 3 (s) to produce CaO(s) and CO 2 (g) has an equilibrium constant at 25°C of 2 × 10 −23 . Values of ΔH ∘ f are as follows: CaCO 3 , −1207.6 kJ/mol; CaO, −634.9 kJ/mol; and CO 2 , −393.5 kJ/mol.
  • What is the equilibrium constant at 900°C?
  • What is the partial pressure of CO 2 (g) in equilibrium with CaO and CaCO 3 at this temperature?
  • Are reactants or products favored at the lower temperature? at the higher temperature?
  • In acidic soils, dissolved Al 3 + undergoes a complex formation reaction with SO 4 2− to form [AlSO 4 + ]. The equilibrium constant at 25°C for the reaction Al 3 + (aq)+SO 4 2− (aq)⇌AlSO 4 + (aq) is 1585.
  • How does this value compare with ΔG° for the reaction Al 3 + (aq)+F − (aq)⇌AlF 2 + (aq), for which K = 10 7 at 25°C?
  • Which is the better ligand to use to trap Al 3 + from the soil?
  • −28.4 kJ/mol
  • −26.1 kJ/mol
  • −19.9 kJ/mol
  • 1.21 × 10 66 ; equilibrium lies far to the right.
  • 1.89 × 10 6 ; equilibrium lies to the right.
  • 5.28 × 10 16 ; equilibrium lies far to the right.
  • 13.3 kJ/mol
  • 5.1 × 10 −21
  • 10.3 kJ/mol
  • 129.5 kJ/mol
  • Products are favored at high T; reactants are favored at low T.

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JEE Main 2024 exam: Important chapters and subject-wise strategy

T he Joint Entrance Examination (JEE) Main is a highly competitive exam that serves as a gateway for aspiring engineers to gain admission into prestigious engineering colleges in India. The Joint Entrance Examination is organised by the National Testing Authority (NTA). The JEE Main exam 2024 is scheduled to commence on January 24, 2024, and go on till February 1, 2024.

Here, Ramesh Batlish, Managing Partner & Head, FIITJEE Noida/G Noida Centre, has curated a list of important chapters and subject-wise strategy for your JEE Main 2024 exam.

IMPORTANT CHAPTERS AND SUBJECT-WISE STRATEGY:  

Important chapters include Mechanics, Fluids, Heat & Thermodynamics, Waves and Sound, Capacitors & Electrostatics, Magnetics, Electromagnetic Induction, Optics and Modern Physics.

However, make sure your concepts are clear on each topic. Solving problems will help you develop concept clarity and improve your confidence level in this subject.

In Physics, solve a problem, then you re-create the problem, re-solve it, change it again, re-solve it again. You will start to notice patterns, and you start asking more complicated questions and will be able to answer those. You repeat until you have a conceptual, quantitative and an intuitive understanding of what's going on.

The more you practice Physics and analyse your mistakes, the better for you. Solve a variety of questions from your coaching modules/study material. The JEE study material must have all the theory and questions as per JEE level.

Important chapters include Qualitative Analysis, Coordination Chemistry & Chemical Bonding in Inorganic Chemistry, Electrochemistry, Thermodynamics, Chemical Equilibrium in Physical Chemistry and Aldehyde & Ketone, Alkyl & Aryl Halides in Organic Chemistry.

Study all reaction mechanisms and remember all named reactions. Make notes while you study each chapter.

For Physical Chemistry, read from NCERT and clear concepts at your coaching institute. After you have studied the chapter, write down all the important formulae of the chapter in a notebook for quick revision before exams.

Complete NCERT thoroughly for solving questions in Inorganic Chemistry. Make precise notes for each chapter.

Mathematics:

Important chapters include Quadratic Equations & Expressions, Complex Numbers, Probability, Vectors & 3D Geometry, Matrices in Algebra; Circle, Parabola, Hyperbola in Coordinate Geometry; Functions, Limits, Continuity and Differentiability, Application of Derivatives, Definite Integral in Calculus.

In this subject, practice is the key. The questions are of excellent quality and will force you to work hard to solve them. The more you study and practice mathematics, the more it develops your analytical and problem-solving skills.

In JEE, mathematics questions are sometimes lengthy, and the options are also close enough, so one must be careful in calculations and time management. The concepts and formulas should be at your fingertips. It is advisable to develop your own shortcuts if possible.

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