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38
Subjective

p-block elements form acidic, basic and amphoteric oxides. Explain each property by giving two examples and also write the reactions of these oxides with water.

Explanation

In p-block, when we move from left to right in a period, the acidic character of the oxides increases due to increase in electronegativity. e.g.,

(i) 2nd period $\mathrm{B}_2 \mathrm{O}_3<\mathrm{CO}_2<\mathrm{N}_2 \mathrm{O}_3$ acidic nature increases.

(ii) 3rd period $\mathrm{Al}_2 \mathrm{O}_3<\mathrm{SiO}_2<\mathrm{P}_4 \mathrm{O}_{10}<\mathrm{SO}_3<\mathrm{Cl}_2 \mathrm{O}_7$ acidic character increases.

On moving down the group, acidic character decreases and basic character increases. e.g.,

(a) Nature of oxides of 13 group elements

$$ \underset{\text { Weakly acidic }}{\mathrm{B}_2 \mathrm{O}_3} \underbrace{\mathrm{Al}_2 \mathrm{O}_3 \quad \mathrm{Ga}_2 \mathrm{O}_3}_{\text {Amphoteric }} \underset{\text { Basic }}{\mathrm{In}_2 \mathrm{O}_3} \underset{\text { Strongly basic}}{\mathrm{Tl}_2 \mathrm{O}} $$

(b) Nature of oxides of 15 group elements

$\underset{\text { Strongly acidic}}{\mathrm{N}_2 \mathrm{O}_5} ~\underset{\text { Moderately acidic}}{\mathrm{P}_4 \mathrm{O}_{10}} ~\underset{\text { Amphoteric}}{\mathrm{As}_4 \mathrm{O}_{10}}~ \underset{\text { Amphoteric}}{\mathrm{Sb}_4 \mathrm{O}_{10}} ~\underset{\text { Basic}}{\mathrm{Bi}_2 \mathrm{O}_3}$

Among the oxides of same element, higher the oxidation state of the element, stronger is the acid. e.g., $\mathrm{SO}_3$ is a stronger acid than $\mathrm{SO}_2$.

$\mathrm{B}_2 \mathrm{O}_3$ is weakly acidic and on dissolution in water, it forms orthoboric acid. Orthoboric acid does not act as a protonic acid (it does not ionise) but acts as a weak Lewis acid.

$$\underset{\text { Boron trioxide }}{\mathrm{B}_2 \mathrm{O}_3}+3 \mathrm{H}_2 \mathrm{O} \rightleftharpoons \underset{\text { Orthoboric acid }}{2 \mathrm{H}_3 \mathrm{BO}_3}$$

$$\mathrm{B}(\mathrm{OH})_3+\mathrm{H}-\mathrm{OH} \longrightarrow\left[\mathrm{B}(\mathrm{OH})_4\right]^{-}+\mathrm{H}^{+}$$

$\mathrm{Al}_2 \mathrm{O}_3$ is amphoteric in nature. It is insoluble in water but dissolves in alkalies and reacts with acids.

$$\underset{\begin{array}{c} \text { Aluminium } \\ \text { trioxide } \end{array}}{\mathrm{Al}_2 \mathrm{O}_3}+2 \mathrm{NaOH} \xrightarrow{\Delta} \underset{\begin{array}{c} \text { Sodium meta } \\ \text { aluminate } \end{array}}{2 \mathrm{NaAlO}_2}+\mathrm{H}_2 \mathrm{O} \longleftarrow \mathrm{Al}_2 \mathrm{O}_3+6 \mathrm{HCl} \xrightarrow{\Delta} \underset{\begin{array}{c} \text { Aluminium } \\ \text { chloride } \end{array}}{2 \mathrm{AlCl}_3}+3 \mathrm{H}_2 \mathrm{O}$$

$$\begin{aligned} &\mathrm{Tl}_2 \mathrm{O} \text { is as basic as } \mathrm{NaOH} \text { due to its lower oxidation state (+1). }\\ &\mathrm{Tl}_2 \mathrm{O}+2 \mathrm{HCl} \longrightarrow 2 \mathrm{TICl}+\mathrm{H}_2 \mathrm{O} \end{aligned}$$

P$$_{4}$$O$$_{10}$$ on reaction with water gives orthophosphoric acid

$$\underset{\begin{array}{c} \text { Phosphorus } \\ \text { pentoxide } \end{array}}{\mathrm{P}_4 \mathrm{O}_{10}}+6 \mathrm{H}_2 \mathrm{O} \longrightarrow \underset{\begin{array}{c} \text { Orthophosphoric } \\ \text { acid } \end{array}}{4 \mathrm{H}_3 \mathrm{PO}_4}$$

$$\begin{aligned} &\mathrm{Cl}_2 \mathrm{O}_7 \text { is strongly acidic in nature and on dissolution in water, it gives perchloric acid. }\\ &\underset{\substack{\text { Dichlorine heptoxide }}}{\mathrm{Cl}_2 \mathrm{O}_7}+\mathrm{H}_2 \mathrm{O} \longrightarrow \underset{\text { Perchloric acid }}{2 \mathrm{HClO}_4} \end{aligned}$$

39
Subjective

How would you explain the fact that the first ionisation enthalpy of sodium is lower than that of magnesium but its second ionisation enthalpy is higher than that of magnesium?

Explanation

First ionisation enthalpy of sodium $\left(\mathrm{Na}=1 s^2, 2 s^2, 2 p^6, 3 s^1\right)$ is lower than that of magnesium $\left(\mathrm{Mg}=1 s^2, 2 s^2 2 p^6, 3 s^2\right)$ because the electron to be removed in both the cases is from 3 s -orbital but the nuclear charge is lower in Na than that of magnesium. After the removal of first electron $\mathrm{Na}^{+}$acquires inert gas $(\mathrm{Ne})$ configuration $\left(\mathrm{Na}^{+}=1 s^2, 2 s^2, 2 p^6\right)$ and hence, removal of second electron from sodium is difficult. While in case of magnesium, after the removal of first electron, the electronic configuration of $\mathrm{Mg}^{+}$is $1 s^2, 2 s^2, 2 p^6, 3 s^1$. In this case $3 s^1$ electron is easy to remove in comparison to remove an electron from inert gas configuration. Therefore, $\mathrm{IE}_2$ of Na is higher than that of magnesium.

40
Subjective

What do you understand by exothermic reaction and endothermic reaction? Give one example of each type.

Explanation

Exothermic reactions Reactions which are accompanied by evolution of heat are called exothermic reactions. The quantity of heat produced is shown either along with the products with a ' + ' sign or in terms if $\Delta H$ with a ' - ' sign. e.g.,

$$\begin{aligned} \mathrm{C}(\mathrm{s})+\mathrm{O}_2(g) & \longrightarrow \mathrm{CO}_2(g)+393.5 \mathrm{~kJ} \\ \mathrm{H}_2(g)+\frac{1}{2} \mathrm{O}_2(g) & \longrightarrow \mathrm{H}_2 \mathrm{O}(l) ; \Delta H=-285.8 \mathrm{~kJ} \mathrm{~mol}^{-1} \end{aligned}$$

Endothermic reactions Reactions which proceed with absorption of heat are called endothermic reactions. The quantity of heat absorbed is shown either along with the products with a ' - ' sign or in terms of $\Delta H$ with a ' + ' sign e.g.,

$$\begin{gathered} \mathrm{C}(\mathrm{s})+\mathrm{H}_2 \mathrm{O}(\mathrm{g}) \longrightarrow \mathrm{CO}(\mathrm{g})+\mathrm{H}_2(g)-131.4 \mathrm{~kJ} \\ \mathrm{~N}_2(g)+3 \mathrm{H}_2(g) \longrightarrow 2 \mathrm{NH}_3(g) ; \Delta H=+92.4 \mathrm{~kJ} \mathrm{~mol}^{-1} \end{gathered}$$

41
Subjective

Arrange the elements $\mathrm{N}, \mathrm{P}, 0$ and S in the order of

(i) increasing first ionisation enthalpy.

(ii) increasing non-metallic character.

Give reason for the arrangement assigned.

Explanation

The placing of elements are as

Period Group-15 Group-16
2nd Period N O
3rd Period P S

(i) Ionisation enthalpy of nitrogen $\left({ }_7 \mathrm{~N}=1 s^2, 2 s^2, 2 p^3\right)$ is greater than oxygen $\left({ }_8 \mathrm{O}=1 s^2\right.$, $2 s^2, 2 p^4$ ) due to extra stable exactly half-filled $2 p$-orbitals. Similarly, ionisation enthalpy of phosphorus $\left({ }_{15} \mathrm{P}=1 s^2, 2 s^2, 2 p^6, 3 s^2, 3 p^3\right)$ is greater than sulphur $\left({ }_{16} \mathrm{~S}=1 s^2, 2 s^2, 2 p^6, 3 s^2, 3 p^4\right)$.

On moving down the group, ionisation enthalpy decreases with increasing atomic size. So, the order is

$$\mathrm{S}<\mathrm{P}<\mathrm{O}<\mathrm{N} \rightarrow \text { First ionisation enthalpy increases. }$$

(ii) Non-metallic character across a period (left to right) increases but on moving down the group it decreases. So, the order is

$\mathrm{P}<\mathrm{S}<\mathrm{N}<\mathrm{O} \rightarrow$ Non-metallic character increases.

42
Subjective

Explain the deviation in ionisation enthalpy of some elements from the general trend by using given figure.

Explanation

There is deviation of ionisation enthalpy of some elements from the general trend as shown in figure. The first ionisation enthalpy of B is lower than that of Be and in case of nitrogen, the first ionisation enthalpy is higher than that of $O$. (Also, refer to Q. 27)