Chemistry Case study (4 Marks)

A process or change is said to be reversible, if a change is brought out in such a way that the process could, at any moment, be reversed by an infinitesimal change. A reversible process proceeds infinitely slowly by a series of equilibrium states such that system and the surroundings are always in near equilibrium with each other. Processes  other than reversible processes are known as irreversible processes.

Isothermal and free expansion of an ideal gas For isothermal (T = constant) expansion of an ideal gas into vacuum; w = 0 since pex = 0. Also, Joule determined experimentally that q = 0; therefore, $\triangle\text{U}=0, \triangle =+\text{Uqw}$ can be expressed for isothermal irreversible and reversible changes as follows:

1. For isothermal irreversible change

$\text{q}=-\text{w}=\text{nRTIn}\frac{\text{V}_\text{f}}{\text{V}_{\text{i}}}$

$=2.303\ \text{nRT}\log\frac{\text{V}_\text{f}}{\text{V}_{\text{i}}}$

2. For isothermal reversible change
3. For adiabatic change, q = 0

$\triangle\text{U}=\text{w}_{\text{ad}}$

In thermodynamics, a distinction is made between extensive properties and intensive properties. An extensive property is a property whose value depends on the quantity or size of matter present in the system. For example, mass, volume, internal energy, enthalpy, heat capacity, etc. are extensive properties. Those properties which do not depend on the quantity or size of matter present are known as intensive properties. For example temperature, density, pressure etc. are intensive properties. A molar property, χm, is the value of an extensive property χ of the system for 1 mol of the substance. If n is the amount of matter, χ χ m = n is independent of the amount of matter. Other examples are molar volume .

Measurement of $\triangle\text{U}$ and $\triangle{Η}$: Calorimetry We can measure energy changes associated with chemical or physical processes by an experimental technique called calorimetry. In calorimetry, the process is carried out in a vessel called calorimeter, which is immersed in a known volume of a liquid. Knowing the heat capacity of the liquid in which calorimeter is immersed and the heat capacity of calorimeter, it is possible to determine the heat evolved in the process by measuring temperature changes. Measurements are made under two different conditions: i) at constant volume, qV ii) at constant pressure, qP

∆U Measurements For chemical reactions, heat absorbed at constant volume, is measured in a bomb calorimeter. Here, a steel vessel (the bomb) is immersed in a water bath. The whole device is called calorimeter. The steel vessel is immersed in water bath to ensure that no heat is lost to the surroundings. A combustible substance is burnt in pure dioxygen supplied in the steel bomb. Heat evolved during the reaction is transferred to the water around the bomb and its temperature is monitored. Since the bomb calorimeter is sealed, its volume does not change i.e., the energy changes associated with reactions are measured at constant volume. Under these conditions, no work is done as the reaction is carried out at constant volume in the bomb calorimeter. Even for reactions involving gases, there is no work done as $\triangle\text{v}=0$ Temperature change of the calorimeter produced by the completed reaction is then converted to qV, by using the known heat capacity of the calorimeter with the help of equation

b)$\triangle{Η}$ Measurements Measurement of heat change at constant pressure (generally under atmospheric pressure) can be done in a calorimeter shown in Figure. We know that $\triangle{Η}=\text{qp}$ (at constant p) and, therefore, heat absorbed or evolved, qP at constant pressure is also called the heat of reaction or enthalpy of reaction, $\triangle\text{rΗ}$ In an exothermic reaction, heat is evolved, and system loses heat to the surroundings. Therefore, qP will be negative and ∆rH will also be negative. Similarly in an endothermic reaction, heat is absorbed, qP is positive and $\triangle\text{rΗ}$ will be positive.

THERMODYNAMICS - NCERT Class 11 Chemistry

1. For adiabatic change, q = 0 then …

1. $\triangle\text{U}=\text{w}_{\text{ad}}$

2. $\triangle\text{U}=\text{q}+\text{w}$

3. $\triangle\text{U}=\text{w}-\text{q}$

4. $\triangle\text{U}=\text{w}_{\text{rev}}$

2. The technique for measure energy changes associated with chemical or physical processes by an experimental technique called …

1. Colourimetry
2. Calorimetry
3. Titration
4. Photometry

3. A property whose value depends on the quantity or size of matter present in the system is known as …

1. Extensive
2. Intensive
3. Reversible
4. Irreversible

4. If there is no work done …

1. V = 0
2. V = 1
3. V = 2
4. V = 3

5. In an endothermic reaction, heat is absorbed, qP  is … and $\triangle\text{rΗ}$ will be …

1. Positive, Positive
2. Negative, Negative
3. Positive, Negative
4. Negative, Positive

Read the passage given below and answer the following questions from (i) to (v).

In a chemical reaction, reactants are converted into products and is represented by, Reactants → Products The enthalpy change accompanying a reaction is called the reaction enthalpy. The enthalpy change of a chemical reaction, is given by the symbol $\triangle\text{rH}.$

$\triangle\text{rH}$ = (sum of enthalpies of products) – (sum  of enthalpies of reactants)

$\sum\limits_\text{t}\text{a}_{\text{t}}\text{H}_\text{products}-\sum\limits_\text{t}\text{b}_\text{t}\text{H}_\text{reactants}$

Here symbol ∑ (sigma) is used for summation and ai and bi  are the stoichiometric coefficients of the products and reactants respectively in the balanced chemical equation. For example, for the reaction

$\text{CH}_4(\text{g})+2\text{O}_2(\text{g})\rightarrow\text{CO}_2(\text{g})+2\text{H}_2\text{O}(\text{l})$

$\triangle_\text{r}\text{H}=\sum\limits_\text{t}\text{a}_{\text{t}}\text{H}_\text{products}-\sum\limits_\text{t}\text{b}_\text{t}\text{H}_\text{reactants}$

$=[\text{H}_\text{m}(\text{CO}_2,\text{g})+2\text{H}_\text{m}(\text{H}_2\text{O},\text{l})]-[\text{H}_\text{m}(\text{CH}_4,\text{g})+2\text{H}_\text{m}(\text{O}_2,\text{g})]$

where H_m is the molar enthalpy. Enthalpy change is a very useful quantity. Knowledge of this quantity is required when one needs to plan the heating or cooling required to maintain an industrial chemical reaction at constant temperature. It is also required to calculate temperature dependence of equilibrium constant.

Standard Enthalpy of Reactions Enthalpy of a reaction depends on the conditions under which a reaction is carried out. It is, therefore, necessary that we must specify some standard conditions. The standard enthalpy of reaction is the enthalpy change for a reaction when all the participating substances are in their standard states. The standard state of a substance at a specified temperature is its pure form at 1 bar. For example, the standard state of liquid ethanol at 298K is pure liquid ethanol at 1 bar; standard state of solid iron at 500K is pure iron at 1 bar. Usually data are taken at 298K. Standard conditions are denoted by adding the superscript 0 to the symbol $\triangle\text{H},$ e.g., $\triangle\text{H}^\phi$

Enthalpy Changes during Phase Transformations Phase transformations also involve energy changes. Ice, for example, requires heat for melting. Normally this melting takes place at constant pressure (atmospheric pressure) and during phase change, temperature remains constant (at 273K).

$\text{H}_2\text{O}(\text{s})\rightarrow\text{H}_2\text{O}(\text{l});\triangle_{\text{fus}}\text{H}^\phi=6.00\text{kJ}\ \text{mol}^{-1}$

Here $\triangle\text{vap}\text{H}^\phi$  is enthalpy of fusion in standard state. If water freezes, then process is reversed and equal amount of heat is given off to the surroundings. The enthalpy change that accompanies melting of one mole of a solid substance in standard state is called standard enthalpy of fusion or molar enthalpy of fusion, $\triangle\text{fus}\text{H}0.$Melting of a solid is endothermic, so all enthalpies of fusion are positive. Water requires heat for evaporation. At constant temperature of its boiling point Tb  and at constant pressure:

$\text{H}_2\text{O}(\text{l})\rightarrow\text{H}_2\text{O}(\text{g});\triangle_{\text{vap}}\text{H}^\phi=+40.79\text{kJ}\ \text{mol}^{-1}$

$\triangle\text{vap}\text{H}^\phi$ is the standard enthalpy of vaporisation. Amount of heat required to vaporize one mole of a liquid at constant temperature and under standard pressure (1bar) is called its standard enthalpy of vaporization or molar enthalpy of vaporization, $\triangle\text{vap}\text{H}^\phi.$ Sublimation is direct conversion of a solid into its vapour. Solid CO₂  or ‘dry ice’ sublimes at 195K with $\triangle\text{sub}\text{H}^\phi=25.2\text{kJ}\text{mol}^{–1};$ naphthalene sublimes slowly and for this $\triangle\text{sub}\text{H}0= 73.0\text{kJ}\text{mol}^{–1}.$ Standard enthalpy of sublimation, $\triangle\text{sub}\text{H}^\phi$ is the change in enthalpy when one mole of a solid substance sublimes at a constant temperature and under standard pressure (1bar). The magnitude of the enthalpy change depends on the strength of the intermolecular interactions in the substance undergoing the phase transfomations. For example, the strong hydrogen bonds between water molecules hold them tightly in liquid phase. For an organic liquid, such as acetone, the intermolecular dipole-dipole interactions are significantly weaker. Thus, it requires less heat to vaporise 1 mol of acetone than it does to vaporize 1mol of water.

Standard Enthalpy of Formation The standard enthalpy change for the formation of one mole of a compound from its elements in their most stable states of aggregation (also known as reference states) is called Standard Molar Enthalpy of Formation. Its symbol is $\triangle\text{f}\text{H}^\phi$ where the subscript ‘ f ’ indicates that one mole of the compound in question has been formed in its standard state from its elements in their most stable states of aggregation. The reference state of an element is its most stable state of aggregation at 25°C and 1 bar pressure.

Hess’s Law of Constant Heat Summation We know that enthalpy is a state function, therefore the change in enthalpy is independent of the path between initial state (reactants) and final state (products). In other words, enthalpy change for a reaction is the same whether it occurs in one step or in a series of steps. This may be stated as follows in the form of Hess’s Law. If a reaction takes place in several steps then its standard reaction enthalpy is the sum of the standard enthalpies of the intermediate reactions into which the overall reaction may be divided at the same temperature. Let us understand the importance of this law with the help of an example. Consider the enthalpy change for the reaction

$\text{C}(\text{graphite,s})+\frac{1}{2}\text{O}_2(\text{g})\rightarrow\text{CO}(\text{g});\triangle_\text{r}\text{H}^{\ominus}=?$

Although CO(g) is the major product, some CO₂  gas is always produced in this reaction. Therefore, we cannot measure enthalpy change for the above reaction directly. However, if we can find some other reactions involving related species, it is possible to calculate the enthalpy change for the above reaction. Let us consider the following reactions:

$\text{C}(\text{graphite,s})+\text{O}_2(\text{g}) \rightarrow\text{CO}_2(\text{g});\triangle\text{r}\text{H}^{\phi}=–393.5\text{kJ}\text{mol}^{–1}(\text{i})$

$\text{CO}(\text{g})+\frac{1}{2}\text{O}_2(\text{g})\rightarrow\text{CO}_2(\text{g})\triangle_\text{r}\text{H}^{\phi}=-283.0\text{kJ}\text{mol}^{-1}(\text{ii})$

We can combine the above two reactions in such a way so as to obtain the desired reaction. To get one mole of CO(g) on the right, we reverse equation (ii). In this, heat is absorbed instead of being released, so we change sign of $\triangle\text{r}\text{H}^\phi$ value

$\text{CO}_2(\text{g})\rightarrow\text{CO}(\text{g})+\frac{1}{2}\text{O}_2(\text{g});\triangle\text{r}\text{H}^{\phi}=+283.0\text{kJ}\text{mol}^{-1}...(\text{iii})$

Adding equation (i) and (iii), we get the desired equation,

$\text{C}(\text{graphite,s})+\frac{1}{2}\text{O}_2(\text{g})\rightarrow\text{CO}(\text{g});$

for which $\triangle_\text{r}\text{H}^{\phi}=(-393.5+283.0)=-110.5\text{kJ}\text{mol}^{-1}$

In general, if enthalpy of an overall reaction A → B along one route is $\triangle\text{rH}$ and$​​\triangle\text{rH}_1,\triangle\text{rH}_2,\triangle\text{rH}_3$ representing enthalpies of reactions leading to same product, B along another route, then we have

$\triangle\text{rH}=​​\triangle\text{rH}_1+\triangle\text{rH}_2+\triangle\text{rH}_3$

It can be represented as:

1. The enthalpy change of a chemical reaction, is given by the symbol …

1. $\triangle\text{rH}$

2. $\triangle\text{rG}$

3. $\triangle\text{rF}$

4. $\triangle\text{rR}$'

2. The molar enthalpy is denoted by:

1. H_k
2. H_m
3. H_l
4. H_n

3. …is enthalpy of fusion in standard state.

1. $\triangle\text{fus}\text{H}^{\phi}$

2. $\triangle_\text{r}\text{H}^{\phi}$

3. $\triangle\text{vap}\text{H}^{\phi}$

4. $\triangle\text{w}\text{H}^{\phi}$

4. Solid CO₂or ‘dry ice’ sublimes at..

1. 100K
2. 195K
3. 150K
4. 200K

5. … is the standard enthalpy of vaporisation.

1. $\triangle\text{fus}\text{H}^{\phi}$

2. $\triangle_\text{r}\text{H}^{\phi}$

3. $\triangle\text{vap}\text{H}^{\phi}$

4. $\triangle\text{w}\text{H}^{\phi}$