\(\mathrm{Ca}_{3}\left(\mathrm{PO}_{4}\right)_{2} \rightleftharpoons 3 \mathrm{Ca}^{2+}_{(aq)}+2 \mathrm{PO}_{4_{(aq)}}^{3-}\\\)
(s)                           (3s)             (2s)
\(K_{sp}=[Ca^{2+}]^{3}[PO_{4}^{3-}]^{2}\)
\(K_{sp}=(3s)^{3}(2s)^{2}\)
\(K_{sp}=27s^{3}.4s^{2}\)
\(K_{sp}=108s^{5}\)
(or)
\(K_{s p} =m^{m} \cdot n^{n} \cdot(s)^{m+n} \)
\(K_{\text {sp }} =3^{3} \cdot 2^{2} \cdot(s)^{3+2} \)
\(K_{s p} =27 \times 4 \times(s)^{5} \)
\(=108(s)^{5}=108 s^{5}\)

A reaction in which the rate is independent of the concentration of the reactant over a wide range of concentration is called a zero order reaction.
Let us consider the following by hypothetical zero order reaction.
 A⟶ product 
The rate law can be written as,
Rate = k[A]⁰ 
\(\frac { -d\left[ A \right] }{ dt } =k(1)\ \ \ \therefore \left( { \left[ A \right] }^{ 0 }=1 \right) \)
\(\Rightarrow -d\left[ A \right] =kdt\)
Integrate the above equation between the limits of [A₀] at zero time and [A] at some later time 't',
\(-\int _{ \left[ { A }_{ 0 } \right] }^{ \left[ A \right] }{ d\left[ A \right] } =k\int _{ 0 }^{ t }{ dt } \)
\(-{ \left( \left[ A \right] \right) }_{ \left[ { A }_{ 0 } \right] }^{ \left[ A \right] }=k{ \left( t \right) }_{ 0 }^{ t }\)
[A₀] - [A] = kt   
\(k=\frac { \left[ { A }_{ 0 } \right] -\left[ A \right] }{ t } \)
Straight line equation y = mx + c
ie., \(\left[ A \right] =-kt+\left[ { A }_{ 0 } \right] \)
⇒ y = c + mx
A plot [A] vs time gives a straight line with a slope of -k and y intercept of [A₀]

(i) \(\mathrm{K}_{\mathrm{w}}=\left[\mathrm{H}_{3} \mathrm{O}^{+}\right]\left[\mathrm{OH}^{-}\right]=1 \times 10^{-14}\left(25^{\circ} \mathrm{C}\right)\)
(ii) Ionic product of water is defined as the product of the concentration of hydronium and hydroxide ions of pure water. Its value at 25^oC is \(1 \times 10^{-14} \mathrm{~mol}^{2} \mathrm{dm}^{-2}\)

(i) First order reaction
(ii) First order reaction
(iii) \(\frac{1}{2}+2=2 \frac{1}{2}\); Pseudo first order reaction

(a) Rate = \(k{ \left[ x \right] }^{ 3/2 }{ \left[ y \right] }^{ 0 }=k[x]^{3/2}\)
(b) 2NO + Br₂ ⟶ 2NOBr
Rate = k[NO]²[Br₂]

Number of atoms in a fcc unit cell = \(\frac{N_{c}}{8}+\frac{N_{f}}{2}=\frac{8}{8}+\frac{6}{2}=1+3=4\)

(i) Ostwald's dilution law relates the dissociation constant of the weak acid (K_a) with its degree of dissociation (α) and the concentration (c).
where  \(\alpha=\frac{\text { Number of moles dissociated }}{\text { Total number of moles }}\)
(ii) The dissociation of acetic acid can be represented as
\(\mathrm{CH}_{3} \mathrm{COOH} \rightleftharpoons \mathrm{H}^{+}+\mathrm{CH}_{3} \mathrm{COO}^{-}\)
The dissociation constant of acetic acid is,
\({ K }_{ a }=\frac { \left[ { H }^{ + } \right] \left[ { CH }_{ 3 }COO^{ - } \right] }{ \left[ { CH }_{ 3 }COOH \right] } \)  ........(1) 

Substituting the equilibrium concentration in equation (1)
\({ K }_{ a }=\cfrac { \left( \alpha C \right) \left( \alpha C \right) }{ \left( 1-\alpha \right) C } \) 
\({ K }_{ a }=\cfrac { { \alpha }^{ 2 }C }{ 1-\alpha } \) .......(2) 
(iii) We know that weak acid dissociates only to a very small extent compared to one, a is so small and hence in the denominator (1 - α) ⋍1. The above expression (2) now becomes,
k_a =a²C \(\Rightarrow { \alpha }^{ 2 }=\cfrac { { k }_{ a } }{ C } \) ; \(\alpha =\sqrt { \cfrac { { K }_{ a } }{ C } } \) 
(iv) When dilution increases, the degree of dissociation of weak electrolyte also increases. This is called Ostwald's dilution law
Also \(;\left[\mathrm{H}^{+}\right]=\alpha \mathrm{C}\) and \(\left[\mathrm{H}^{+}\right]=\left(\sqrt{\frac{\mathrm{K}_{\mathrm{a}}}{\mathrm{C}}}\right) \mathrm{C}=\sqrt{\frac{\mathrm{K}_{\mathrm{a}} \mathrm{C}^{2}}{\mathrm{C}}}=\sqrt{\mathrm{K}_{\mathrm{a}} \cdot \mathrm{C}}\)
Similarly for a weak base
\(\begin{aligned} & \mathrm{K}_{\mathrm{b}}=\alpha^2 \mathrm{C} ; \quad \therefore \alpha=\sqrt{\frac{\mathrm{k}_{\mathrm{b}}}{\mathrm{C}}}, \\ \end{aligned}\)
\(\begin{aligned} & {\left[\mathrm{OH}^{-}\right] \alpha \mathrm{C}=\sqrt{\frac{\mathrm{K}_{\mathrm{b}}}{\mathrm{C}}} \times \mathrm{C}=\sqrt{\frac{\mathrm{K}_{\mathrm{b}} \mathrm{C}^2}{\mathrm{C}}}=\sqrt{\mathrm{K}_{\mathrm{b}} \mathrm{C}}} \end{aligned}\)

(i) Collision theory is based on the kinetic theory of gases. According to this theory, a chemical reaction occurs as a result of collisions between the reacting molecules.
(ii) Let us understand this theory by considering the following reaction.
A₂(g) + B₂(g) ⟶ 2AB(g)
(iii) If we consider that, the reaction between A₂ and B₂ molecules proceeds through collisions between them, then the rate would be proportional to the number of collisions per second.
(iv) Rate ∝ number of molecules colliding per litre per second (collision rate).
(v) The number of collisions is directly proportional to the concentration of both A₂ and B₂.
Collison rate ∝ [A₂][B₂]
Collision rate = Z [A₂][B₂]
(vi) Where, Z is a constant
(vii) A fraction of effective collisions (f) is given by the following expression
\(f={ e }^{ \frac { { -E }_{ a } }{ RT } }\)
(xiv) This fraction of collisions is further reduced due to orientation factor i.e., even if the reactant collides with sufficient energy, they will not react unless the orientation of the reactant molecules is suitable for the formation of the transition state.
(viii) The diagram illustrates the importance of proper alignment of molecules which leads to reaction.

(ix) The fraction of effective collisions (f) having proper orientation is given by the steric factor p.
⇒ Rate = p x f x collision rate
\(\Rightarrow Rate=p\times { e }^{ \frac { -Ea }{ RT } }\times Z\left[ { A }_{ 2 } \right] \left[ { B }_{ 2 } \right] \quad ...(1)\)
As per the rate law,
Rate = \(k=\left[ { A }_{ 2 } \right] \left[ { B }_{ 2 } \right] \quad ...(2)\)
Where k is the rate constant
On comparing equation (1) and (2), the rate constant k is
\(k=pZ{ e }^{ \frac { -Ea }{ RT } }\)

In bcc unit cell, ΔABC
AC² = AB² + BC²
\(AC=\sqrt { { AB }^{ 2 }+{ BC }^{ 2 } } \)
\(\\ AC=\sqrt { { a }^{ 2 }+{ a }^{ 2 } } =\sqrt { { 2a }^{ 2 } } =\sqrt { 2 } a\)

In ΔACG
AG² = AC² + CG²
\(AG=\sqrt { { AC }^{ 2 }+{ CG }^{ 2 } } \)
\(AG=\sqrt { { \left( \sqrt { 2a } \right) }^{ 2 }+{ a }^{ 2 } } \)
\(AG=\sqrt { { 2a }^{ 2 }+{ a }^{ 2 } } =\sqrt { { 3a }^{ 2 } } \)
\(AG=\sqrt { 3a } \)
\(\sqrt { 3 } a=4r\)
\(r=\frac { \sqrt { 3 } }{ 4 } a\)
∴ Volume of the sphere with radius 'r' \(=\frac { 4 }{ 3 } { \pi r }^{ 3 }\)
\(=\frac{4}{3}\pi { \left( \frac { \sqrt { 3 } }{ 4 } a \right) }^{ 3 }\)\(=\frac { \sqrt { 3 } }{ 16 } \pi { a }^{ 3 }\)
Number of spheres belong to a unit cell in BCC arrangement is equal to two and hence the total volume of all spheres.
(i) Packing fraction = \(=\frac{Total \quad volume \quad occupied \quad by \quad spheres \quad in \quad a \quad unit \quad cell}{volume \quad of \quad the \quad unit \quad cell}\times100\)
\(\therefore\)Volume of all spheres \(=2\times \left( \frac { \sqrt { 3 } \pi { a }^{ 3 } }{ 16 } \right) =\frac { \sqrt { 3 } \pi { a }^{ 3 } }{ 8 } \)
Packing fraction \(=\frac { \left( \frac { \sqrt { 3 } \pi { a }^{ 3 } }{ 8 } \right) }{ ({ a }^{ 3 }) } \times 100\)
\(=\frac { \sqrt { 3 } \pi }{ 8 } \times 100\)
\(\\ =\sqrt { 3 } \pi \times 12.5\)
= 1.732 x 3.14 x 12.5
= 68%

Basic buffer is the solution which has weak base and its salt.
NH₄OH + HCI → NH₄CI +H₂O + NH₄OH
200 ml   100 ml    salt       100 ml  weak base

BaSO₄ ⇌ Ba²⁺ + SO₄^2-
K_sp = (s) (s)
K_sp = (s)²
= (2.42 × 10^-3gL^-1)²
\(=\frac{2.42 \times 10^{-3} gL^{-1}}{233 \text{ g mol}^{-1}}\)
= (0.01038 x 10^-3)²
= (1.038 x  x 10^-5)²
= 1.077 x 10^-10
= 1.08 × 10^-10mol²L^-2

(rate constant K is equal to collision frequency A if E_a = 0)
In zero order reactions, increase in the concentration of reactant does not alter the rate.
So statement (i) is wrong.
\(k=A{ e }^{ -\left( \frac { { E }_{ a } }{ RT } \right) }\)
if E_a = 0 so, statement (ii) is correct, and statement (iii) is wrong
k = Ae⁰
k = A
In k = In A - \({ \left( \frac { { E }_{ a } }{ R } \right) }\) \(\left( \frac { 1 }{ T } \right) \)
This equation is of the form of a straight line y = mx+c
A plot of In k Vs \(\left( \frac { 1 }{ T } \right) \) gives a straight line with a negative slope
So statement (iv) and (v) are wrong.

\(k=A{ e }^{ -\left( \frac { { E }_{ a } }{ RT } \right) }\)
In k = In A - \({ \left( \frac { { E }_{ a } }{ R } \right) }\) \(\left( \frac { 1 }{ T } \right) \)
This equation is of the form of a straight line y = mx+c
A plot of In k Vs \(\left( \frac { 1 }{ T } \right) \) gives a straight line with a negative slope.

In bcc unit cell,
2 atoms = 1 unit cell
Number of atoms in 8 g of element is, Number of moles = 8g / 40 g mol^-1 = 0.2 mol
1 mole contains 6.023 x10²³ atoms 
0.2 mole contains 0.2 x 6.023 x 10²³ atoms
[1 unit cell / 2 atoms] x 0.2 x 6.023 x 10²³
= 6.023 x 10²² unit cells.

Number of A ions = N_c/8 = 8/8 = 1
Number of B ions = N_f/2 = 6/2 = 3
Simplest formula = AB₃