Q.A sparingly soluble salt having general formula A_x^{p+} B_y^{q-} and molar solubility S is in equilibrium with its saturated solution. Derive a relationship between the solubility and solubility product for such salt.
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🔒 Start your 14-day free trial to unlock the full solution →Concept understanding — Solubility Product Constant
Solubility Product Constant: From Intuition to Precision
Imagine you drop a pinch of salt into a glass of water. The salt crystals disappear — they dissolve. But what if you keep adding salt, spoonful after spoonful? At some point, the water can't hold any more; the extra salt just sits at the bottom, undissolved. That's a saturated solution — the maximum amount of solute has dissolved at that temperature.
Now, here's the key question: even in that saturated solution, is everything static? Not at all. At the microscopic level, salt ions are constantly leaving the solid crystal and entering the solution (dissolving), while other ions in solution bump into the crystal and stick back (precipitating). At saturation, these two processes happen at exactly the same rate. The system is in dynamic equilibrium.
A saturated solution is not "full" in a static sense — it's a busy, balanced dance between dissolving and precipitating.
The Intuition: A Crowded Dance Floor
Think of a dance hall with a capacity limit. The "dancers" are ions (like Na⁺ and Cl⁻ from table salt). The dance floor is the solution. When the floor is empty, dancers easily find space — dissolution is fast. As more dancers arrive, they start bumping into each other and some leave the floor (precipitate). At the maximum capacity, the number of dancers entering equals the number leaving. That equilibrium number of dancers is what we call solubility.
But here's the twist: for many salts, the "dancers" come in different types — say, positive ions and negative ions. The equilibrium isn't just about the total number; it's about the product of their concentrations. Why product? Because the chance of a positive and a negative ion meeting to form a solid depends on both their concentrations. If you double the concentration of positive ions, the chance of a collision doubles. If you double both, it quadruples.
That product — at equilibrium, for a saturated solution — is a constant. That's the solubility product constant, Ksp.
The Precise Statement
For a sparingly soluble salt that dissociates in water as:
AmBn(s)⇌mAn+(aq)+nBm−(aq)
the solubility product constant is defined as:
Ksp=[An+]m⋅[Bm−]n
where the square brackets denote molar concentrations (mol/L) at saturation (equilibrium with the solid).
The solid AmBn does not appear in the expression. Its concentration is constant (pure solid) and is absorbed into Ksp. Never write [AmBn] in the Ksp expression.
What Ksp Tells You
- Small Ksp (e.g., 10−30): The salt is very insoluble. Only a tiny amount dissolves.
- Large Ksp (e.g., 10−2): The salt is relatively soluble.
- Ksp is temperature-dependent — always quote the temperature (usually 25°C).
Ksp is an equilibrium constant. It only applies to saturated solutions in contact with undissolved solid. If no solid is present, the solution may be unsaturated (Q<Ksp) or supersaturated (Q>Ksp), but Ksp itself doesn't change.
A Concrete Example: Silver Chloride
Silver chloride, AgCl, is a classic sparingly soluble salt. Its dissolution:
AgCl(s)⇌Ag+(aq)+Cl−(aq)
The Ksp expression:
Ksp=[Ag+][Cl−]
At 25°C, Ksp=1.8×10−10. This tiny number means that in a saturated solution, the product of the two ion concentrations is only 1.8×10−10.
If you know the solubility of AgCl is s mol/L, then [Ag+]=s and [Cl−]=s, so: …
The Solubility Product Constant (Ksp) is the equilibrium constant for the dissolution of a sparingly soluble ionic compound in a saturated solution. It quantifies the extent to which the salt dissolves.
For a sparingly soluble salt with the general formula AxBy, its dissolution equilibrium is:
AxBy(s)⇌xAp+(aq)+yBq−(aq)
If the molar solubility of the salt is S mol/L, then at equilibrium, the concentration of the ions will be:
[Ap+]=xS
[Bq−]=yS
The solubility product constant is defined as the product of the molar concentrations of the ions, each raised to the power of its stoichiometric coefficient: …
For a sparingly soluble salt Axp+Byq− with molar solubility S, the solubility product constant Ksp is given by Ksp=xxyySx+y.
When a salt is described as "sparingly soluble," it means that only a very small amount of it dissolves in a solvent, typically water, to form a solution. Despite this small amount, an equilibrium is established between the undissolved solid salt and its constituent ions in the saturated solution. This equilibrium is crucial for understanding the behavior of such salts.
The solubility product constant (Ksp) is an equilibrium constant that quantifies this equilibrium. It represents the product of the concentrations of the ions in a saturated solution, each raised to the power of its stoichiometric coefficient in the balanced dissolution equation. Because it's an equilibrium constant, Ksp has a constant value at a given temperature for a specific salt.
The molar solubility (S) of a salt, on the other hand, is a measure of how much of the salt dissolves. Specifically, it is defined as the number of moles of the salt that dissolve per liter of solution to form a saturated solution. The relationship between Ksp and S allows us to calculate one if the other is known, providing a quantitative way to describe the solubility of these salts.
Let's derive this relationship step-by-step for a general salt Axp+Byq−.
- Write the Dissociation Equilibrium: The salt Axp+Byq− dissociates in water to form its respective ions. The balanced chemical equation for this dissolution equilibrium is:
AxBy(s)⇌xAp+(aq)+yBq−(aq)
Here, $A_x B_y (s)$ represents the solid salt, and $A^{p+} (aq)$ and $B^{q-} (aq)$ represent the aqueous ions. The coefficients $x$ and $y$ are the stoichiometric coefficients for the cation and anion, respectively.
2. Define Molar Solubility (S) and Relate it to Ion Concentrations:
Let S be the molar solubility of the salt AxBy. This means that in a saturated solution, S moles of AxBy dissolve per liter of solution.
From the balanced dissociation equation, for every 1 mole of AxBy that dissolves, x moles of Ap+ ions and y moles of Bq− ions are produced.
Therefore, if S moles of AxBy dissolve:
* The concentration of the cation Ap+ will be [Ap+]=xS
* The concentration of the anion Bq− will be [Bq−]=yS
> [!WARNING]
> A common mistake is to forget the stoichiometric coefficients when determining the ion concentrations from the molar solubility $S$. For example, if the salt were $CaF_2$, then $S$ moles of $CaF_2$ would yield $S$ moles of $Ca^{2+}$ and $2S$ moles of $F^-$. …
Showing the 12 most recent of 13 on this concept.
- TG EAPCET 2026Set eng-2026-05-09-AN1 markMCQQ.Gold number of a protective colloid (A) is x. A mixture is prepared by adding 50 mL of 10% NaCl solution to 500 mL of gold sol. What is the minimum mass (in mg) of A to be added to the solution to prevent the coagulation of gold sol? (A) 50x (B) 500x (C) 5x (D) 0.5x
›Reveal solutionSolution
Gold number is defined for 10 mL sol +1 mL of 10% NaCl; here both sol and NaCl are scaled up ×50, so mass needed =50x mg.
The gold number x = milligrams of protective colloid A that just prevents coagulation of 10 mL of standard gold sol on adding 1 mL of 10% NaCl.
In this problem:
gold sol=500 mL=50×10 mL,10% NaCl=50 mL=50×1 mL …
- TG EAPCET 2026Set eng-2026-05-10-AN1 markMCQQ.AB crystallizes in a bcc lattice. If the distance between two oppositely charged ions in the lattice is 335 pm, then the edge length of it (in pm) is (A) 376.8 (B) 366.8 (C) 386.8 (D) 396.8
›Reveal solutionSolution
In a body-centered cubic (bcc) lattice of a compound AB, the distance between oppositely charged ions is half the body diagonal, so the edge length is a=32×335≈386.8 pm, matching option (C).
Concept & Intuition
The key is to visualize the geometry of a bcc lattice. In AB crystallizing in bcc, the ions are arranged such that one type (say A) sits at the corners and the other (B) at the body center, or vice versa. The shortest distance between an A and a B ion is along the body diagonal — from a corner to the center of the cube. That distance is exactly half the length of the full body diagonal. The body diagonal of a cube of edge length a is 3a. So if the given distance (335 pm) is that half-diagonal, we can solve for a.
Step-by-step solution
-
Identify the relevant distance
In a bcc lattice, the closest oppositely charged ions are a corner ion and the body-centered ion. The distance between them is half the body diagonal of the cube.
-
Write the relationship
Body diagonal of a cube = 3a.
Half of that = 23a.
This is given as 335 pm:
23a=335
- Solve for edge length a Multiply both sides by 2:
3a=670
Divide by 3:
a=3670… -
- TG EAPCET 2025Set eng-2025-05-04-FN1 markMCQQ.100 mL of 0.05 M Cu2+ aqueous solution is added to 1 L of 0.1 M KI solution. The number of moles of I2 and CuI2 formed are respectively (A) 5×10−3, 2.5×10−3 (B) 5×10−3, 5×10−3 (C) 2.5×10−3, 2.5×10−3 (D) 2.5×10−3, 5×10−3
›Reveal solutionSolution
2Cu²⁺+4I⁻→Cu₂I₂+I₂; 5×10⁻³ mol Cu²⁺ gives 2.5×10⁻³ mol each of I₂ and the precipitate.
Cu²⁺ does not form a stable CuI₂; it oxidises I⁻ and is itself reduced to Cu(I), precipitating as Cu₂I₂: 2Cu²⁺ + 4I⁻ → Cu₂I₂ + I₂. n(Cu²⁺)=0.100×0.05=5×10⁻³ mol is limiting (I⁻ = 1×0.1 = 0.1 mol, large excess). For every 2 mol Cu²⁺, 1 mol I₂ and 1 m …
- TG EAPCET 2023Set ap-2023-05-11-FN1 markMCQQ.The ratio of radii of second orbits of Li2+ and Be3+ is (A) 4:3 (B) 2:3 (C) 3:2 (D) 3:4
›Reveal solutionSolution
The radius of an electron's orbit in a hydrogen-like atom is directly proportional to the square of the principal quantum number (n2) and inversely proportional to the atomic number (Z). For the second orbits of Li2+ and Be3+, the ratio of their radii is 4:3.
The problem asks for the ratio of the radii of the second orbits of two hydrogen-like species: Li2+ and Be3+. To solve this, we need to understand how the radius of an electron's orbit is determined in such systems.
Concept and Intuition
Bohr's model, while having limitations, accurately describes the energy and radii of orbits for hydrogen and hydrogen-like species (atoms or ions with only one electron). Both Li2+ (Lithium with 3 protons, losing 2 electrons leaves 1 electron) and Be3+ (Beryllium with 4 protons, losing 3 electrons leaves 1 electron) are hydrogen-like species.
According to Bohr's model, the radius of the n-th orbit (rn) for a hydrogen-like atom with atomic number Z is given by a specific formula. This formula shows that the radius depends on two main factors:
- The principal quantum number (n), which defines the energy level or orbit. Higher n means larger orbits.
- The atomic number (Z), which represents the number of protons in the nucleus. A higher Z means a stronger attractive force from the nucleus, pulling the electron closer and resulting in smaller orbits.
The relationship is that rn is directly proportional to n2 and inversely proportional to Z. This proportionality is crucial for calculating ratios, as many constants cancel out.
The radius of the n-th orbit in a hydrogen-like atom is given by:
rn=πme2Zϵ0h2n2=0.529Zn2 A˚
where ϵ0 is the permittivity of free space, h is Planck's constant, m is the mass of the electron, e is the elementary charge, n is the principal quantum number, and Z is the atomic number.
For ratio calculations, we can simply use the proportionality:
rn∝Zn2
Let's apply this understanding to find the required ratio.
Step-by-step Solution
- Identify the relevant parameters for Li2+:
- For Lithium (Li), the atomic number Z=3.
- The problem specifies the "second orbit", so the principal quantum number n=2.
- Using the proportionality rn∝Zn2, the radius of the second orbit for Li2+ can be expressed as: …
- TG EAPCET 2023Set eng-2023-05-13-AN1 markMCQQ.At T (K), Kc value for the reaction $\frac{1}{3} \mathrm{N}_2(g) + \mathrm{H}_2(g) \rightleftharpoons \frac{2}{3} \mathrm{NH}_3 (g)is50.TheK_cvalueforthereaction2\mathrm{NH}_3(g) \rightleftharpoons \mathrm{N}_2(g) + 3\mathrm{H}_2 (g)atthesametemperatureis(A)4 \times 10^{-6}(B)8 \times 10^{-6}(C)6 \times 10^{-6}(D)8 \times 10^{-3}$
›Reveal solutionSolution
The key idea is to relate equilibrium constants when the reaction is reversed and scaled. Given Kc=50 for 31N2+H2⇌32NH3, the Kc for 2NH3⇌N2+3H2 is 8×10−6.
Concept and Intuition
Equilibrium constants depend on how the reaction is written. If you multiply a reaction by a factor, the Kc is raised to that power. If you reverse a reaction, Kc becomes its reciprocal. Here, the target reaction is the reverse of the given reaction, but also multiplied by 3 to clear fractions. So we need to apply both transformations.
Step-by-step solution
- Write the given reaction and its Kc Given:
31N2(g)+H2(g)⇌32NH3(g)Kc1=50
- Reverse the reaction Reversing gives:
32NH3(g)⇌31N2(g)+H2(g)
For a reversed reaction, Kc becomes the reciprocal:
Kc,reverse=Kc11=501
- Multiply the reversed reaction by 3 to clear fractions Multiply every coefficient by 3:
2NH3(g)⇌N2(g)+3H2(g)
When a reaction is multiplied by a factor n, the equilibrium constant is raised to the nth power. Here n=3, so: …
- TG EAPCET 2022Set ap-2022-07-30-FN1 markMCQQ.The number of Schottky defects present in NaCl per cm3 at room temperature is (A) 103 (B) 1023 (C) 1016 (D) 106
›Reveal solutionSolution
Schottky defects are thermally-activated vacancies that occur in ionic crystals. At room temperature, the equilibrium concentration follows Arrhenius behavior, yielding approximately 106 defects per cm³ in NaCl.
Understanding Schottky Defects
A Schottky defect occurs when a pair of ions (one cation and one anion) are missing from their lattice sites in an ionic crystal, maintaining electrical neutrality. These defects form spontaneously due to thermal energy and represent an equilibrium between the entropy gain from disorder and the energy cost of creating vacancies.
The key insight is that defect concentration is governed by thermodynamics, not kinetics. Even though creating a vacancy requires energy, at any finite temperature, some defects will exist because they increase the entropy of the crystal.
Calculating Equilibrium Defect Concentration
The number of Schottky defects follows the Arrhenius equation:
n=Nexp(−2kBTEs)
where:
- n = number of Schottky defects per unit volume
- N = number of lattice sites per unit volume
- Es = energy to form one Schottky defect pair
- kB = Boltzmann constant
- T = absolute temperature
1. Determine the number of lattice sites (N)
For NaCl, there are approximately 2×1022 ion pairs per cm³ (this comes from the density and molar volume of NaCl).
2. Identify the formation energy (Es)
For NaCl, the Schottky defect formation energy is approximately Es≈2 eV (this is an experimentally determined value).
3. Apply room temperature conditions
At room temperature (T≈300 K):
- kBT≈0.026 eV
- Therefore: 2kBTEs=2×0.0262≈38
4. Calculate the defect fraction
Nn=exp(−38)≈3×10−17
5. Find the absolute number of defects …
- TG EAPCET 2022Set eng-2022-07-19-AN1 markMCQQ.Match the following.
[!FORMULA] Metal SulfideA) PbSB) HgSC) MnSD) ZnSSolubility productI) 4.0×10−53II) 8.0×10−28III) 1.6×10−24IV) 2.5×10−13
The correct match is (A) A B C D \quad I II III IV (B) A B C D \quad I IV II III (C) A B C D \quad III IV I II (D) A B C D \quad III IV II I›Reveal solutionSolution
The solubility product Ksp of a metal sulfide depends on the solubility of the sulfide in water, which is linked to the position of the metal in the qualitative analysis scheme. The order of increasing Ksp is PbS < HgS < ZnS < MnS, matching A→I, B→II, C→IV, D→III, so the correct option is (B).
The key concept here is solubility product and its relation to the qualitative analysis of cations. In the classical H₂S scheme, metal sulfides precipitate at different pH values because their Ksp values vary enormously. The less soluble the sulfide, the smaller its Ksp. PbS and HgS are very insoluble (Group II in the H₂S scheme), while MnS is much more soluble (Group IV). ZnS sits in between (Group II but soluble in dilute acid). So the order of increasing Ksp (from smallest to largest) is: PbS < HgS < ZnS < MnS.
Now let’s match the given numbers to this order.
-
Identify the smallest Ksp.
The smallest value among the four is 4.0×10−53 (I). This must belong to the most insoluble sulfide. Between PbS and HgS, HgS is famously the least soluble — its Ksp is astronomically small. So HgS → I is a strong candidate. But let’s check: PbS has Ksp≈10−28 range, so indeed HgS gets the 10−53 value. So B → I.
-
Next smallest Ksp.
The next smallest is 8.0×10−28 (II). This fits PbS, which is very insoluble but not as extreme as HgS. So A → II.
-
The two larger Ksp values. …
-
- TG EAPCET 2021Set ap-2021-08-09-FN1 markMCQQ.The ratio of packing density in FCC, BCC, simple cubic and HCP, respectively, is (A) 0.7:0.92:1.0:1.0 (B) 1.0:0.7:0.92:1.0 (C) 1.0:0.92:0.7:1.0 (D) 0.92:0.5:1.0:0.92
›Reveal solutionSolution
The packing densities are FCC = 0.74, HCP = 0.74, BCC = 0.68, simple cubic = 0.52.
Their ratio in the order FCC : BCC : simple cubic : HCP is 0.74 : 0.68 : 0.52 : 0.74, which simplifies to 1.0 : 0.92 : 0.7 : 1.0.
The correct option is (C).
Concept & Intuition
Packing density (or atomic packing factor, APF) is the fraction of volume in a crystal structure that is actually occupied by atoms. It depends on two things: how many atoms are in a unit cell, and how efficiently they fill space. For hard spheres of equal size, the densest possible packing is 0.74 — achieved by both FCC and HCP. BCC is slightly less dense (0.68), and simple cubic is the loosest (0.52). The question asks for the ratio of these values in the order FCC, BCC, simple cubic, HCP. So we just compute each APF and compare.
Step-by-step reasoning
-
Simple cubic (SC)
- One atom per unit cell (8 corners × 1/8).
- Edge length a=2r (atoms touch along the edge).
- Volume of atom = 34πr3, cell volume = a3=8r3.
- APF = 8r31×34πr3=6π≈0.5236.
-
Body-centered cubic (BCC)
- 2 atoms per unit cell (1 center + 8 corners × 1/8).
- Atoms touch along the body diagonal: 3a=4r → a=34r.
- Cell volume = a3=3364r3.
- APF = 64r3/(33)2×34πr3=8π3≈0.6802.
-
Face-centered cubic (FCC)
- 4 atoms per unit cell (6 face centers × 1/2 + 8 corners × 1/8).
- Atoms touch along the face diagonal: 2a=4r → a=24r=22r.
- Cell volume = a3=162r3.
- APF = 162r34×34πr3=32π≈0.7405.
-
Hexagonal close-packed (HCP)
- For ideal HCP (c/a ratio = 8/3≈1.633), the packing density is the same as FCC: 0.7405.
- Reason: both are close-packed structures; the difference is only in stacking order (ABCABC vs ABAB), not in the fraction of filled space.
-
Form the ratio …
-
- TG EAPCET 2021Set eng-2021-08-04-AN1 markMCQQ.Potassium crystallizes in FCC lattice with unit cell length of 0.5 nm. The approximate density (in g cm−3), if it contains 0.1% Schottky defects is (A) 1.2 (B) 2.1 (C) 1.7 (D) 2.8
›Reveal solutionSolution
Schottky defects reduce the effective number of atoms in a unit cell, thereby decreasing the crystal's density. For potassium in an FCC lattice with 0.1% Schottky defects, the approximate density is 2.1 g/cm3.
Concept and Intuition
- Crystal Lattice and Unit Cell: Potassium crystallizes in a Face-Centered Cubic (FCC) lattice. In an FCC unit cell, atoms are located at all eight corners and the center of each of the six faces. The effective number of atoms belonging to one FCC unit cell (Z) is calculated as (8×81)+(6×21)=1+3=4.
- Density of a Crystal: The density (ρ) of a crystalline solid is determined by the total mass of atoms within a unit cell divided by the volume of the unit cell. The mass of the unit cell is the number of atoms (Z) multiplied by the mass of a single atom (Molar mass M divided by Avogadro's number NA). The volume of a cubic unit cell is a3, where a is the unit cell length.
- Schottky Defects: A Schottky defect is a type of point defect in a crystal lattice where an atom (or an ion pair in ionic crystals) is missing from its regular lattice site, creating a vacancy.
- The presence of these missing atoms means that the total mass within a given volume of the crystal is less than that of a perfect crystal.
- Consequently, Schottky defects decrease the overall density of the crystal.
- If a crystal has x% Schottky defects, it implies that x% of the lattice sites are vacant, and thus, the effective number of atoms contributing to the mass of the unit cell is reduced by x%.
Step-by-Step Solution
-
Identify Given Values and Constants:
- Lattice type: FCC, so the number of atoms per unit cell for a perfect crystal (Z) is 4.
- Unit cell length (a) = 0.5 nm.
- Percentage of Schottky defects = 0.1%.
- Molar mass of Potassium (M) = 39 g/mol (standard atomic weight).
- Avogadro's number (NA) = 6.022×1023 mol−1.
-
Convert Unit Cell Length to Centimeters:
The density is required in g cm−3, so we convert the unit cell length from nanometers to centimeters:
a=0.5 nm=0.5×10−9 m=0.5×10−7 cm.
-
Calculate the Volume of the Unit Cell:
For a cubic unit cell, the volume (V) is a3:
V=(0.5×10−7 cm)3=0.125×10−21 cm3.
-
Determine the Effective Number of Atoms per Unit Cell (Z′) with Schottky Defects:
A 0.1% Schottky defect means that 0.1% of the lattice sites are vacant. This directly translates to a 0.1% reduction in the effective number of atoms present in the unit cell.
Fraction of defects = 0.1%=1000.1=0.001.
The effective number of atoms per unit cell (Z′) is:
Z′=Z×(1−fraction of defects)
Z′=4×(1−0.001)=4×0.999=3.996. …
- TG EAPCET 2021Set eng-2021-08-04-FN1 markMCQQ.If the molar concentrations of base and its conjugate acid are same, then pOH of the buffer solution is (A) same as pKb of base (B) same as pKa of base (C) same as pKa of acid (D) same as pKb of acid
›Reveal solutionSolution
When the molar concentrations of a weak base and its conjugate acid are equal in a buffer, the Henderson–Hasselbalch equation for bases gives pOH=pKb of the base. The correct option is (A).
The key here is the Henderson–Hasselbalch equation for a basic buffer. A buffer made from a weak base and its conjugate acid (the salt of that base) resists changes in pH. The equation that governs its pOH is:
pOH=pKb+log[base][conjugate acid]
This is the direct analogue of the acid-buffer equation pH=pKa+log[acid][conjugate base]. The logic is identical: the ratio of the two species determines how far the pOH is from the base's pKb.
Now, the problem states that the molar concentrations of the base and its conjugate acid are the same. That means [base]=[conjugate acid], so the ratio [base][conjugate acid]=1.
- Plug this into the Henderson–Hasselbalch equation for bases:
pOH=pKb+log(1)
- Since log(1)=0, the equation simplifies immediately to:
pOH=pKb
That’s the entire reasoning — no further calculation needed. The pOH of the buffer equals the pKb of the weak base when the two components are at equal concentration. …
- TG EAPCET 2021Set eng-2021-08-04-FN1 markMCQQ.If the density of a 2 M solution of ethylene glycol in water is 1.11 g/ml, the molality (in 'm') of the solution is approximately (A) 1.92 (B) 1.57 (C) 2.05 (D) 2.15
›Reveal solutionSolution
Take 1 L of solution: mass =1110 g, solute =124 g, water =986 g; molality =2/0.986≈2.05 m.
Take exactly 1 L of the 2 M solution.
- Moles of ethylene glycol (C2H6O2, M=62 g/mol) =2 mol.
- Mass of solute =2×62=124 g.
- Mass of solution =1000 mL×1.11 g/mL=1110 g. …
- TG EAPCET 2021Set eng-2021-08-05-AN1 markMCQQ.The ratio of the highest to the lowest wavelength of Lyman series is (A) 4:3 (B) 9:8 (C) 27:5 (D) 16:5
›Reveal solutionSolution
The highest wavelength in the Lyman series corresponds to the smallest energy transition (n=2 to n=1), while the lowest wavelength corresponds to the largest energy transition (n=∞ to n=1). The ratio of these wavelengths is 4:3.
Concept and Intuition
When an electron in a hydrogen atom (or a hydrogen-like ion) jumps from a higher energy level to a lower one, it emits a photon. The energy of this photon corresponds to the energy difference between the two levels, and this energy determines the photon's wavelength.
The energy levels in a hydrogen atom are quantized, given by En=−n213.6 eV, where n is the principal quantum number (n=1,2,3,…).
The energy of the emitted photon is ΔE=Eni−Enf, where ni is the initial (higher) energy level and nf is the final (lower) energy level.
This energy is also related to the wavelength λ by the equation ΔE=λhc, where h is Planck's constant and c is the speed of light.
From this, we see that λ=ΔEhc. This means:
- A larger energy difference (ΔE) results in a shorter wavelength (λ).
- A smaller energy difference (ΔE) results in a longer wavelength (λ).
The Lyman series specifically refers to transitions where electrons fall to the ground state, meaning the final energy level is nf=1. The initial energy level ni can be 2,3,4,…,∞.
To find the highest wavelength (λmax) in the Lyman series, we need the smallest possible energy difference. This occurs for the transition from ni=2 to nf=1.
To find the lowest wavelength (λmin) in the Lyman series, we need the largest possible energy difference. This occurs for the transition from ni=∞ (the ionization limit) to nf=1.
We can use the Rydberg formula, which directly relates the wavelength of emitted light to the principal quantum numbers of the initial and final states.
The Rydberg formula for the wavelength λ of spectral lines in a hydrogen atom is given by:
λ1=R(nf21−ni21)
where R is the Rydberg constant, nf is the principal quantum number of the final energy level, and ni is the principal quantum number of the initial energy level (ni>nf).
Step-by-step Derivation
- Identify the Lyman series parameters: For the Lyman series, electrons transition to the ground state. Therefore, the final principal quantum number is nf=1. The Rydberg formula for the Lyman series becomes:
λ1=R(121−ni21)=R(1−ni21)
- Calculate the highest wavelength (λmax): The highest wavelength corresponds to the smallest energy transition. For the Lyman series (nf=1), the smallest energy transition occurs when the electron falls from the very next higher level, which is ni=2. Substitute ni=2 into the Rydberg formula: λmax1=R(1−221) …
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