Author: impushpshikha

  • For the autoionization of water at 25°C, what is ΔG° for the process?

    Pure water captured in a transparent glass

    For the autoionization of water at 25°C,

    H2O (l) ⟺ H+(aq) + OH (aq)

    kw= 1.0 × 10-14 . What is ΔG° for this process?

    Interpretation

    The autoionization of water is the process in which a small fraction of water molecules transfer a proton to one another, producing hydrogen and hydroxide ions:\(\mathrm{H_2O(l)\rightleftharpoons H^+(aq)+OH^-(aq)}\)

    The key idea in this problem is the connection between equilibrium and thermodynamics. The equilibrium constant tells us how far a reaction proceeds, while the standard Gibbs free energy change tells us whether the reaction is thermodynamically favorable under standard conditions.

    These quantities are related by:\(\Delta G^\circ = -RT\ln K\)

    where:\(R = 8.314\ \mathrm{J,mol^{-1},K^{-1}}\)

    and

    \(T\) is the absolute temperature.

    Because the ionization constant of water is extremely small,\(K_w = 1.0\times10^{-14}\)

    we already expect the forward reaction to be unfavorable under standard conditions. Therefore, the answer should come out as a positive value of \(\Delta G^\circ\).


    Concept Application

    For the given equilibrium,\(\mathrm{H_2O(l)\rightleftharpoons H^+(aq)+OH^-(aq)}\)

    the equilibrium constant is:\(K = K_w = 1.0\times10^{-14}\)

    The temperature is:\(T = 25^\circ\mathrm{C} = 298.15\ \mathrm{K}\)

    Substituting these values into the Gibbs free energy equation will directly give the standard free energy change for the autoionization process.


    Solution

    Using\(\Delta G^\circ = -RT\ln K_w\)

    Substituting the numerical values,\(\Delta G^\circ = -(8.314)(298.15)\ln(1.0\times10^{-14})\)

    Now evaluate the logarithmic term:\(\ln(1.0\times10^{-14}) = -14\ln 10\)

    Since\(\ln 10 = 2.303\)

    we obtain\(\ln(1.0\times10^{-14}) = -14(2.303) = -32.24\)

    Substituting back,\(\Delta G^\circ = -(8.314)(298.15)(-32.24)\)\(\Delta G^\circ = 79.9\times10^4\ \mathrm{J,mol^{-1}}\)

    Converting joules to kilojoules,\(\Delta G^\circ = 79.9\ \mathrm{kJmol^{-1}}\)

    Therefore,\(\Delta G^\circ = +79.9\ \mathrm{kJmol^{-1}}\)


    Insight

    A useful relationship to remember is:

    • If \(K>1\), then \(\Delta G^\circ<0\)
    • If \(K<1\), then \(\Delta G^\circ>0\)

    Since water has an extremely small ionization constant, \(K_w=10^{-14}\), the equilibrium lies overwhelmingly toward molecular water. The large positive value of \(\Delta G^\circ\) is simply the thermodynamic expression of that fact.

    Final Answer:\(\\Delta G^\circ = +79.9\ \mathrm{kJmol^{-1}}\)

  • A 110.0 g piece of zinc at 95.0°C is placed into 60.0 g of water inside a 100.0 g calorimeter at 20.0°C. Given the specific heat capacities of zinc (0.377 kJ/kg°C) and the calorimeter (0.419 kJ/kg°C), determine the final temperature of the system once it reaches thermal equilibrium.

    A piece of zinc submerged in water

    A 110.0 g piece of zinc at 95.0°C is placed into 60.0 g of water inside a 100.0 g calorimeter at 20.0°C. Given the specific heat capacities of zinc (0.377 kJ/kg°C) and the calorimeter (0.419 kJ/kg°C), determine the final temperature of the system once it reaches thermal equilibrium.

    Interpretation

    This problem is a classic application of calorimetry, which is based on one of the most important ideas in thermodynamics: energy is conserved.

    When a hot object and a cold object are brought into thermal contact inside an insulated system, heat does not disappear; it simply flows from the hotter body to the colder one until a common temperature is reached. That common temperature is called the thermal equilibrium temperature.

    In this case:

    • The zinc sample starts at 95.0C95.0^\circ\text{C}, so it will lose heat.
    • The water and the calorimeter start at 20.0C20.0^\circ\text{C}, so they will gain heat.
    • No heat is assumed to escape to the surroundings.

    Therefore,

    Heat lost by zinc=Heat gained by water+Heat gained by calorimeter\text{Heat lost by zinc} = \text{Heat gained by water} + \text{Heat gained by calorimeter}

    A common mistake is to include only the water. The calorimeter also absorbs heat, so its heat capacity must be included in the energy balance.


    Concept Application

    The amount of heat exchanged by a substance is given byq=mcΔTq = mc\Delta Twhere:

    • mm = mass
    • cc = specific heat capacity
    • ΔT\Delta T = temperature change

    Notice that zinc cools while water and the calorimeter warm. Rather than worrying about signs, it is often clearer to write:

    Heat lost=Heat gained\text{Heat lost} = \text{Heat gained}

    and use positive quantities for each.

    The specific heats are given in

    kJ kg1C1\text{kJ kg}^{-1}\!^\circ\text{C}^{-1}

    Since

    1 kJ kg1C1=1 J g1C1,1\ \text{kJ kg}^{-1}\!^\circ\text{C}^{-1} = 1\ \text{J g}^{-1}\!^\circ\text{C}^{-1},

    we may conveniently work with masses in grams.

    For water,

    cw=4.184 J g1C1c_w = 4.184\ \text{J g}^{-1}\!^\circ\text{C}^{-1}

    For zinc,

    cZn=0.377 J g1C1c_{\text{Zn}} = 0.377\ \text{J g}^{-1}\!^\circ\text{C}^{-1}

    For the calorimeter,

    ccal=0.419 J g1C1c_{\text{cal}} = 0.419\ \text{J g}^{-1}\!^\circ\text{C}^{-1}

    Solution

    Step 1: Write the heat-balance equation

    Heat lost by zinc:qZn=(110)(0.377)(95Tf)q_{\text{Zn}} = (110)(0.377)(95-T_f)

    Heat gained by water:qw=(60)(4.184)(Tf20)q_w = (60)(4.184)(T_f-20)

    Heat gained by calorimeter:qcal=(100)(0.419)(Tf20)q_{\text{cal}} = (100)(0.419)(T_f-20)

    Applying conservation of energy:(110)(0.377)(95−Tf​)=(60)(4.184)(Tf​−20)+(100)(0.419)(Tf​−20)


    Step 2: Simplify the coefficients

    For zinc:110×0.377=41.47110 \times 0.377 = 41.47

    For water:60×4.184=251.0460 \times 4.184 = 251.04

    For the calorimeter:100×0.419=41.90100 \times 0.419 = 41.90

    Substituting:41.47(95Tf)=251.04(Tf20)+41.90(Tf20)41.47(95-T_f) = 251.04(T_f-20) + 41.90(T_f-20)

    Combining the right-hand side:41.47(95Tf)=292.94(Tf20)41.47(95-T_f) = 292.94(T_f-20)


    Step 3: Expand both sides

    3939.6541.47Tf=292.94Tf5858.83939.65 – 41.47T_f = 292.94T_f – 5858.8

    Bring all temperature terms to one side:3939.65+5858.8=292.94Tf+41.47Tf3939.65 + 5858.8 = 292.94T_f + 41.47T_f9798.45=334.41Tf9798.45 = 334.41T_f


    Step 4: Solve for the final temperature

    Tf=9798.45334.41T_f = \frac{9798.45}{334.41}Tf=29.3CT_f = 29.3^\circ\text{C}


    Final Answer

    Tf=29.3C\boxed{T_f = 29.3^\circ\text{C}}

    Thus, after thermal equilibrium is established, the zinc, the water, and the calorimeter all reach a common temperature of approximately29.3C.\boxed{29.3^\circ\text{C}}.


    Insight

    A powerful way to check your answer is to compare the heat capacities of the objects:mcZn=(110)(0.377)41.5 J/Cm c_{\text{Zn}} = (110)(0.377) \approx 41.5\ \text{J}/^\circ\text{C}

    whilemcwater+mccal=251.0+41.9293 J/Cm c_{\text{water}} + m c_{\text{cal}} = 251.0 + 41.9 \approx 293\ \text{J}/^\circ\text{C}

    The water–calorimeter system can absorb about seven times more heat per degree than the zinc can release per degree. Therefore, the final temperature should stay much closer to 20C20^\circ\text{C} than to 95C95^\circ\text{C}. The calculated value of 29.3C29.3^\circ\text{C} is exactly what we would expect physically.

    Memory aid: In calorimetry, do not focus first on masses—focus on mcmc, the heat capacity. The object with the larger heat capacity has the greater influence on the final equilibrium temperature.

  • Equilibrium in Chemistry: Concept, Equilibrium Constant Formula & Significance

    A balanced state where opposing processes occur at equal rates, maintaining constant concentrations of reactants and products.

    Interpretation

    In chemistry, equilibrium is not just a definition; it is a natural principle that governs how systems behave. Whether it is a chemical reaction, a physical change, or even a biological regulation, systems tend to move toward a state where opposing processes balance each other.

    At its core, equilibrium means no observable change with time, but this does not mean that everything has stopped. Instead, it reflects a perfect balance of opposing tendencies. This distinction is important because many students mistakenly think equilibrium is a static condition, when in reality it is often highly dynamic at the microscopic level.


    Concept Application

    Let us connect this idea to chemical systems.

    In most chemical reactions, the process does not simply stop after forming products. Instead, as products accumulate, they begin to react backward to reform reactants. This creates two competing processes:

    • Forward reaction: Reactants → Products
    • Reverse reaction: Products → Reactants

    Equilibrium is reached when these two processes occur at equal rates.

    At this point:

    • Concentrations of reactants and products become constant
    • The reaction appears to have stopped
    • But molecular activity continues continuously

    This understanding allows us to classify equilibrium meaningfully.


    What is Equilibrium?

    Equilibrium is the state of a system in which no net change occurs with time, because opposing processes exactly balance each other. Even if the system is disturbed, natural tendencies act to restore this balance.

    This idea extends beyond chemistry. For instance, a book resting on a table remains stationary because the downward gravitational force is exactly balanced by the upward normal force. Such a balance ensures stability.

    Thus, equilibrium represents a condition of perfect balance between opposing influences, leading to a stable system.


    Types of Equilibrium

    Equilibrium can broadly be understood in two forms:


    1. Dynamic Equilibrium

    Dynamic equilibrium applies to both physical and chemical processes. It occurs when two opposite processes happen at the same rate.

    Consider a closed container containing water:\(\text{H}_2\text{O (l)} \rightleftharpoons \text{H}_2\text{O (g)}\)

    • Water molecules continuously evaporate into vapor
    • Simultaneously, vapor molecules condense back into liquid
    • When both rates become equal, equilibrium is established

    At this stage:

    • The amount of liquid and vapor remains constant
    • But molecules are continuously exchanging between phases

    This is why it is called dynamic equilibrium; there is continuous activity, yet no visible change.


    2. Chemical Equilibrium

    Chemical equilibrium specifically refers to reversible chemical reactions: \(\text{Reactants} \rightleftharpoons \text{Products}\)

    Initially, the forward reaction dominates. As products form, the reverse reaction begins. Eventually, a state is reached where:\(\text{Rate of forward reaction} = \text{Rate of reverse reaction}\)

    At equilibrium:

    • Concentrations remain constant
    • Reactions continue at the molecular level
    • The system is stable but not static

    Types Based on Phases

    1. Homogeneous Equilibrium
      All species are in the same phase:\(\text{N}_2 (g) + 3\text{H}_2 (g) \rightleftharpoons 2\text{NH}_3 (g)\)
    2. Heterogeneous Equilibrium
      Different phases are involved:\(\text{CaCO}_3 (s) \rightleftharpoons \text{CaO} (s) + \text{CO}_2 (g)\)

    Equilibrium Constant (K)

    To describe equilibrium quantitatively, we use the equilibrium constant.

    For a general reaction:\(aA + bB \rightleftharpoons cC + dD\)

    The equilibrium constant is:\(K = \frac{[C]^c [D]^d}{[A]^a [B]^b}\)

    This expression tells us the relative amounts of products and reactants at equilibrium.

    For gaseous systems:

    • In terms of concentration → \(K_c\)
    • In terms of pressure → \(K_p\)

    Their relationship is:\(K_p = K_c (RT)^{\Delta n}\)

    Where

    Δn=moles of gaseous productsmoles of gaseous reactants\Delta n = \text{moles of gaseous products} – \text{moles of gaseous reactants}

    If \(\Delta n = 0\), then:\(K_p = K_c\)

    Also, pure solids and liquids are not included in equilibrium expressions because their effective concentration remains constant.


    Significance of Equilibrium Constant

    The value of \(K\) tells us how far a reaction proceeds:

    • \(K \gg 1\) → Products are favored; reaction proceeds nearly to completion
    • \(K \ll 1\) → Reactants are favored; very little product forms
    • \(K \approx 1\) → Both reactants and products are present in comparable amounts

    Thus, \(K\) acts as a measure of the position of equilibrium.


    Insight

    A powerful way to remember equilibrium is this:

    Equilibrium is not about stopping; it is about balancing.

    Also keep in mind:

    • Equal rates do not mean equal concentrations
    • A large \(K\) does not mean fast reaction—it only indicates extent, not speed

    If you internalize these two ideas, equilibrium will start to feel intuitive rather than abstract.

  • Hess’s Law

    Hess’s law

    Introduction

    Think about traveling from Delhi to Mumbai. You might go by train, bus, or airplane. The journey may differ in route and experience, but the starting point and destination remain the same, so the overall displacement does not change.

    A similar idea appears in everyday physics. If you move from the first floor to the fourth floor of a building, you may go directly or stop at intermediate floors. Regardless of the path, the total gain in gravitational potential energy is the same because it depends only on where you start and where you end.

    Chemical reactions follow this same principle.

    When reactants are converted into products, the total energy change, specifically the enthalpy change depends only on the initial state (reactants)and the final state (products). It does not matter whether the reaction occurs in one step or through several intermediate steps.

    This powerful idea is formalized in Hess’s Law, proposed by the Swiss chemist Germain Hess.


    Statement of Hess’s Law

    Hess’s Law states:

    The total enthalpy change \(ΔH\) for a chemical reaction is the same whether the reaction occurs in a single step or in multiple steps.

    In other words, if a reaction can be expressed as the sum of several smaller reactions, then:\(ΔHoverall​=ΔH1​+ΔH2​+ΔH3​+⋯\)

    This works because enthalpy is a state function.


    Understanding the Key Idea: State Function

    A state function is a property that depends only on the current state of the system, not on how the system reached that state.

    Enthalpy is one such property. Therefore:\(ΔH=Hproducts​−Hreactants​\)

    This expression tells us something important: once the initial and final states are fixed, the value of \(ΔH\) is fixed. The path taken in between becomes irrelevant.


    What Does Enthalpy Change Represent?

    The enthalpy change \(ΔH\) represents the heat absorbed or released at constant pressure.

    • If \(ΔH<0\), heat is released (exothermic reaction)
    • If \(ΔH>0\), heat is absorbed (endothermic reaction)

    Since enthalpy is a state function, this heat change depends only on the initial and final conditions, not on the reaction pathway.


    Illustration with a Chemical Reaction

    Let us apply Hess’s Law to a real example.

    We want to determine the enthalpy change for the formation of carbon monoxide:

    C(s)+12O2(g)CO(g),ΔH=110.0kJ/mol\text{C}(s) + \frac{1}{2}\text{O}_2(g) \rightarrow \text{CO}(g),ΔH=−110.0 kJ/mol

    Direct measurement of this reaction is not easy. So instead, we use known reactions:

    C(s)+O2(g)CO2(g),ΔH=393.5kJ/mol\text{C}(s) + \text{O}_2(g) \rightarrow \text{CO}_2(g),ΔH=−393.5 kJ/mol
    CO(s)+12O2(g)CO2(g),ΔH=283.0kJ/mol\text{CO}(s) + \frac{1}{2}\text{O}_2(g) \rightarrow \text{CO}_2(g),ΔH=−283.0 kJ/mol

    Our goal is to obtain the target reaction.

    We notice that in equation (b), CO appears as a reactant, but in our target reaction, CO must be a product.

    So we reverse equation (b).


    Step 1: Reverse the Reaction

    CO2(g)CO(s)+12O2(g) ,ΔH=+283.0kJ/mol\text{CO}_2(g)\rightarrow \text{CO}(s) + \frac{1}{2}\text{O}_2(g) \ ,ΔH=+283.0 kJ/mol

    Why did the sign change?

    Because reversing a reaction reverses the direction of heat flow. A reaction that originally released heat will now require the same amount of heat.


    Step 2: Add the Equations

    Now, add equation (a) and the reversed (b):\(C(s)+O2​(g)→CO2​(g)\)

    CO2(g)CO(g)+12O2(g)\text{CO}_2(g)\rightarrow \text{CO}(g) + \frac{1}{2}\text{O}_2(g)

    Cancel species that appear on both sides:

    • \(CO2​(g)\) cancels out
    • One-half of \(O2​(g)\) remains

    The final equation becomes:

    C(s)+12O2(g)CO(g)\text{C}(s) + \frac{1}{2}\text{O}_2(g) \rightarrow \text{CO}(g)

    Step 3: Add Enthalpy Changes\(ΔH=(−393.5)+(283.0)=−110.5 kJ/mol\)

    This matches the enthalpy change for the direct formation of CO.


    Algebraic Rules for Applying Hess’s Law

    Hess’s Law works like algebra, and the rules are logical once you see why they exist:

    • Reversing a reaction changes the sign of \(ΔH\), because heat flow reverses.
    • Multiplying a reaction multiplies \(ΔH\), since energy is an extensive property.
    • Adding reactions means adding their enthalpy changes.
    • Common species cancel, just like terms in equations, because they do not affect the net change.

    Conclusion

    Hess’s Law teaches a powerful and elegant idea:
    Energy changes depend only on where a reaction starts and where it ends—not on how it gets there.

    This allows chemists to calculate enthalpy changes for reactions that are difficult or impossible to measure directly.

    Once you internalize this, Hess’s Law stops being a formula to memorize and becomes a logical tool—almost like solving a puzzle where energy must always balance perfectly.

  • Write equilibrium constant expressions kc and kp for reversible reactions.

    Equilibrium constants Kc and kp

    Interpretation

    At equilibrium, we express the equilibrium constant in terms of concentrations (\(K_c\)) or partial pressures (\(K_p\)) using the law of mass action.

    However, there is a crucial refinement students must internalize:

    Pure solids and pure liquids do not appear in equilibrium expressions because their concentrations (or activities) remain constant and are taken as unity.

    This is not a shortcut—it reflects physical reality. A solid’s “effective concentration” does not change during the reaction, so including it would not affect the equilibrium ratio.

    For gases:

    Use \(K_c\) in terms of molar concentration
    Use \(K_p\) in terms of partial pressures
    They are related by:

    \(K_p=K_c (RT)^{\Delta n}\)

    where \(\Delta n = \text{moles of gaseous products} – \text{moles of gaseous reactants}\)


    Concept Application

    For each reaction, we will:

    Identify phases carefully
    Exclude solids and liquids

    Include only:
    gases (for both \(K_c\) and \(K_p\))
    aqueous species (only in \(K_c\))
    Compute \(\Delta n\) only using gaseous species (for \(K_p\))


    Solution


    (1) 3Fe (s) + 4H₂O (g) ⇌ Fe₃O₄ (s) + 4H₂ (g)

    Only gases are included: H₂O(g) and H₂(g)

    \(K_c = \frac{[H_2]^4}{[H_2O]^4}\)

    For \(K_p\):

    \(K_p = \frac{(P_{H_2})^4}{(P_{H_2O})^4}\)

    Now check \(\Delta n\):

    \(\Delta n = 4 – 4 = 0\)

    So,

    \(K_p = K_c\)


    (2) HF (aq) + H₂O (l) ⇌ H₃O⁺ (aq) + F⁻ (aq)

    Here:

    H₂O is a pure liquid → excluded
    All others are aqueous species

    \(K_c = \frac{[H_3O^+][F^-]}{[HF]}\)

    No \(K_p\) expression exists because there are no gaseous species.


    (3) 4NH₃ (g) + 5O₂ (g) ⇌ 4NO (g) + 6H₂O (g)

    All species are gases → all are included

    \(K_c = \frac{[NO]^4 [H_2O]^6}{[NH_3]^4 [O_2]^5}\)

    \(K_p = \frac{(P_{NO})^4 (P_{H_2O})^6}{(P_{NH_3})^4 (P_{O_2})^5}\)

    Now compute \(\Delta n\):

    \(\Delta n = (4+6) – (4+5) = 10 – 9 = 1\)

    So,

    \(K_p = K_c (RT)^1 = K_c RT\)


    (4) P₄ (s) + 6Cl₂ (g) ⇌ 4PCl₃ (l)

    P₄ is a solid → excluded
    PCl₃ is a liquid → excluded
    Only Cl₂(g) remains

    \(K_c = \frac{1}{[Cl_2]^6}\)

    \(K_p = \frac{1}{(P_{Cl_2})^6}\)

    Now,

    \(\Delta n = 0 – 6 = -6\)

    So,

    \(K_p = K_c (RT)^{-6}\)


    Insight

    The fastest way to get these right in exams is to build a mental filter:

    “If it’s a solid or liquid → ignore it. If it’s gas or aqueous → include it.”

    Also remember:

    If only one gaseous species appears, it will sit alone in the denominator or numerator—this often surprises students.
    When \(\Delta n = 0\), \(K_p = K_c\), which is a powerful shortcut worth spotting instantly.

    If you consistently apply these filters, equilibrium expressions stop being memorization—and become almost automatic.

  • What is Calorimetry?

    What is Calorimetry?

    Calorimetry is a technique which we use to measure the amount of heat released or absorbed during a reaction. To measure the heat of a reaction accurately, it is essential to isolate the system to avoid heat exchange with the environment. We accomplish this using a device known as a calorimeter.

    Calorimeter mainly consists of metallic vessels which are good conductor of heat such as aluminium and copper etc. The vessel includes a built-in stirring mechanism to mix its contents. This vessel is placed inside an insulated jacket to minimize heat loss to the surroundings. A single opening is provided for inserting a thermometer to monitor temperature changes during the reaction.

    Principle of Calorimetry

    The principle of calorimetry is based on the law of conservation of energy, which states that energy cannot be created or destroyed, only transferred from one body to another. When two objects at different temperatures come into contact, the object at the higher temperature transfers heat energy to the one at the lower temperature. This heat transfer continues until both objects reach the same temperature, a state known as thermal equilibrium.

    Example

    Consider a scenario where someone places a hot iron rod into a container of cool water. Since the iron rod is at a higher temperature and the water is at a lower temperature, heat will transfer from the rod to the water.

    As a result:

    • The temperature of the iron rod decreases.
    • The temperature of the water increases.

    This exchange of heat continues until both the rod and the water reach the same final temperature. According to the principle of calorimetry, the total heat lost by the hot object is equal to the total heat gained by the cooler one. Mathematically, we express it as follows:

    qwater + qiron rod = 0

    By rearranging this gives:

    qwater = – qiron rod

    Here, q represent the amount of heat transferred, we calculate it using the formula:

    q = mcΔT

    Where:

    • m is the mass of the substance (in grams),
    • c is the specific heat capacity (a material-specific constant),
    • ΔT is the change in temperature, calculated as:

    ΔT =Tfinal – Tinitial

    Where, Tfinal is final temperature and Tinitial is initial temperature.

    This formula allows us to quantify the heat exchanged between substances during thermal interactions and is fundamental in calorimetry calculations.

    Types of Calorimeter

    1. Bomb Calorimeter
    2. Coffee cup calorimeter

    Let’s discuss about these calorimeter in detail:

    1. Bomb Calorimeter: A bomb calorimeter is a device used to measure the heat of combustion of a substance. It functions based on the principle of calorimetry and operates by burning a sample in a sealed chamber filled with high-pressure oxygen at constant volume. Scientists refer to this sealed chamber as the “bomb” due to its design, which can withstand the force generated during combustion. In most bomb calorimeters, water surrounds the chamber as it absorbs the heat released during combustion process.
    2. Coffee cup Calorimeter: This calorimeter is a simple yet effective tool for measuring heat transfer during chemical reactions in liquid solutions. It operates at constant pressure and typically consists of two nested Styrofoam coffee cups with a lid to provide thermal insulation. Laboratories frequently use this type of calorimeter due to its convenience, affordability, and suitability for basic thermochemical experiments.

    Applications

    1. Food technologists can determine the energy content of food by measuring the heat released during combustion using calorimeter in food laboratories.
    2. Researchers can determine the specific heat capacity of a material by measuring the heat exchanged during temperature changes using calorimeter.
    3. Calorimetry is useful for analyzing medicines and other biological substances by measuring heat changes during molecular interactions, helping to understand their properties and effects.

    Limitations

    1. Assuming the solution is pure water:
    • In reactions involving aqueous solutions (like acids and bases), we often assume the solution has the same density (1 g/mL) and specific heat capacity (4.18 J/g°C) as water.
    • However, if the solution contains dissolved substances (like salts or acids), its actual properties may differ, leading to inaccuracies.

    2. Assuming no heat is lost to the surroundings:

    • In reality, some heat is always lost to the container or environment, especially in simple calorimeters like coffee cup calorimeters.
    • This causes the measured temperature change to be smaller than it would be in a perfectly insulated system, underestimating the true heat change.

  • Calculate Kp for the reaction H2 (g) + I2 (g) ⇄ 2HI (g) at 25°C

    Calculate Kp for the reaction H2 (g) + I2 (g) ⇄ 2HI (g) at 25°C

    Calculate Kp for the below reaction at 25°C:

    Solution:

    Interpretation: We will use the equation that describes the relation between equilibrium constant (Kp ) and Gibb’s free energy change (ΔG°).

    ΔG° = – RTlnKp

    Where, ΔG° = Standard free energy change

    Kp = Equilibrium constant in terms of pressure

    Given: ΔG° = 2.60 kJ/mol

    Solution: ΔG° = – RTlnKp

    Therefore, Kp for the reaction, H2 (g) + I2 (g) ⇄ 2HI (g) is 0.35 .

  • What is Gibb’s free energy?

    What is Gibb’s free energy?

    The concept of Gibbs free energy was developed by the American scientist Josiah Willard Gibbs. Initially, he termed it “available energy” to evaluate the spontaneity of chemical reactions in relation to change in entropy and enthalpy within the system. We denote Gibbs free energy by symbol “G”.

    Moreover, this energy is a state function, which means that it depends solely on the system’s current condition and is independent of the pathway taken to reach that condition.

    Formula

    Gibbs free energy is defined as the difference between the system’s enthalpy and the product of the temperature and the system’s entropy.

    G = H -TS

    Where,

    G = Gibbs free energy

    H = Enthalpy

    T = Temperature

    S = Entropy

    Gibbs Free Energy Change

    It is a thermodynamical quantity that gives the free energy at standard experimental conditions. As a result, to name the energy of a thermodynamic system as standard free energy, the reactants and products of that system should be at the standard conditions.

    ΔG = ΔH – TΔS

    Where, ΔG = Gibbs free energy change

    ΔH = Enthalpy change

    T = Temperature (in Kelvin)

    ΔS = Entropy change

    Gibbs free energy change and spontaneity

    This energy is utilized to determine whether a reaction is spontaneous, non-spontaneous, or at equilibrium.

    To proceed, we will apply ΔG formula to calculate the desired value of ΔG:

    ΔG = ΔH – TΔS

    Therefore, by determining ΔG, we can classify the process as spontaneous, non-spontaneous, or at equilibrium, based on the provided table.

    ΔGInterpretation
    ΔG>0Reaction is non – spontaneous
    (reaction is endergonic)
    ΔG<0Reaction is spontaneous (reaction is exergonic)
    ΔG=0The system is at equilibrium (there is no net change either in forward or reverse direction)

    Effects of delta H, delta S and T on spontaneity

    CaseΔHΔSΔGSpontaneity (yes/No)
    I+++(at low T)
    -(at high T)
    No (at low T)
    Yes (at high T)
    II++ (at all T)No
    III+– (at all T)Yes
    IV– (at low T)
    + (at high T)
    Yes (at low T)
    No (at high T)

    Example:

    Using the values of ΔH and ΔS, predict which of the following reactions will be spontaneous at 25°C:

    Reaction A: ΔH = 10.5 kJ/mol, ΔS = 30 J/K·mol

    If the reaction is non-spontaneous at 25°C, determine the temperature at which it may become spontaneous.

    Solution

    Interpretation: A spontaneous reaction is one that releases energy, and so the sign of ΔG must be negative. Change in free energy ΔG is defined as, ΔG = ΔH – TΔS .

    We have given the reaction with specific ΔH and ΔS values at a particular temperature, we will calculate the ΔG value using the formula provided. Subsequently, this will enable us to determine the spontaneity of the reaction.

    Reaction A: ΔH =10.5 kJ/mol , ΔS = 30 J/K.mol ,

    Temperature = 25 +273 = 298

    ΔG = ΔH – TΔS

    Since ΔG is positive, Reaction A is non-spontaneous. However, the reaction can become spontaneous when the temperature exceeds 25°C, as ΔG may become negative at that temperature, indicating spontaneity.

    Standard state free energy change for a reaction

    The standard free energy change for a reaction, represented by ΔG°rxn, is defined as the difference in the standard free energies of formation between the products and reactants. Therefore, it serves as an indicator of the reaction’s spontaneity under standard conditions.

    We can calculate standard free energy change by using the following formula:

    Where , ΔG°rxn = Standard entropy change for reaction

    n = stoichiometry coefficient for product

    m =stoichiometry coefficient for reactant

    = sum of

    Example: For reaction :

    In order to find ΔG°rxn , we will use this formula:

    Therefore, ΔG°rxn for the reaction  is 2 Mg (s) + O2 (g) → 2 MgO(s) is 1139 kJ/mol.

    Relation between Gibbs free energy (delta G) and Equilibrium constant (K)

    Let’s consider the following reversible reaction as

    A + B  ⇌  C + D

    The relation between delta G and equilibrium constant for the given reaction as:

    ΔG=ΔG°+RTlnQ

    Where, ΔG = Free energy

    ΔG° = Change in standard free energy

    R = ideal gas constant ( 8.314 J/mol.K)

    T = Absolute temperature in Kelvin

    Q = reaction Quotient

    At Equilibrium ΔG = 0, Q = Keq

    [ Keq for above reaction is :

    So, the relation at equilibrium is:

    0 = ΔG° + RT ln Keq

    ΔG° = – RT ln Keq

    Consequently, The equation  ΔG° = – RT ln Keq , describes the relation between ΔG°(standard free energy change) and Keq (Equilibrium constant). Specifically, R = Gas Constant and T = Absolute Temperature.

    In chemistry, this equation is a fundamental relation in thermodynamics, as it allows us to determine the equilibrium constant of a reaction when the change in standard free energy is known, and vice versa.