Review of Basic Concepts in Analytical Chemistry

Percent Concentrations

Weight percent, (w/w)

= mass solute x 100% mass solution temperature invariant same units for numerator and denominator

Volume percent, (v/v)

= volume solute x 100% volume solution same units for numerator and denominator

Weight/volume percent, (w/v)

= mass solute, g x 100% volume solution, mL

Note:
units have to be specified

parts per million

for dilute solutions = mass solute x 106 mass solution = mg/L

parts per billion

= mass solute x 109 mass solution = g/mL

Example: 4 -21 Skoog, 8th ed.

a. b. c. d. e. f. g. h.

C KCl.MgCl2 = 1.037 x 10-2 M [Mg2+] = 1.037 x 10-2 M [Cl-] = 3.11 x 10-2 M %w/v of KClMgCl26H2O = 0.288 % (w/v) mmol Cl- = 0.778 mmol ppm K+ = 405 ppm pMg = 1.984 pCl = 1.507

Review of Basic Concepts in Analytical Chemistry

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Ionic Equilibria Calculations

Activity, ax
effective concentration arises from transient electrostatic interactions between ions in solution attraction between unlike charges brings ions closer together and behave as neutral molecules Important in equilibrium calculations explains behavior of strong electrolytes

Relationship between activity and concentration

ax = x[x] where x = activity coefficient [x] = concentration

Activity coefficient
depends on concentration of all ions in solution x unity as [x] zero since the probability of interactions decreases with decreasing concentration of ions

Properties of Activity Coefficients

1.

explains non-ideal behavior of electrolytes Ionic strength is minimal in very dilute solutions

(x 1) x decreases with increasing ionic strength at moderate ionic strength: x< 1 at infinite dilution, x 1, ax [x]

Properties of Activity Coefficients

2. Ionic strength determines the value of x NOT the nature of the electrolyte

3. x is dependent on the magnitude of the

electrical charge on the ion, NOT on the sign of the charge. The higher the charge of an ion, the farter x is from unity.

Properties of Activity Coefficients

4.

5.

The size of the hydrated ions affects x Smaller ions show greater departure for ideal behavior vs. larger ions at the same ionic strength. Ions have less effect on the activity of neutral molecules than upon another electrolyte.

6.

x describes behavior of ion x in all equilibria

in which it participates

Ionic strength,
property of a solution that depends on the total concentration of ions in solution, and on the charge carried by each of these ions = [MiZi2] where Mi= molar concentration of ion i Zi = charge on ion I Note: for very dilute solutions: m 0 x 1 ax Cx

Calculate the ionic strengths of the following solutions:

1. 2. 3.

0.10 M NaCl 0.10 M Al2(SO4)3 0.15 M HCl + 0.15 M NiCl2

Ionic strengths:
1. 2. 3.

0.10 M NaCl = 0.10 M 0.10 M Al2(SO4)3 = 1.50 M 0.15 M HCl + 0.15 M NiCl2 = 0.60 M

Debye-Hckel Equation
-log x = 0.51Zx2 1 + 3.3 ax where it the effective diameter of hydrated ion x in nanometers, 10-9 m

Debye-Hckel Limiting Law

-log x = 0.51Zx2 for low ionic strength solutions ( < 0.01 M)

Calculate Fe2+using the DHL

given that = 0.75 and aFe2+ = 0.9

Ans. = 0.20

Review of Basic Concepts in Analytical Chemistry

Chemical Equilibrium

Types of Equilibrium Constants: Thermodynamic (K)

mathematical description of equilibrium condition Consider the reaction

mA + nB pC + qD K = (aC)p(aD)q (aA)m(aB)n at 25oC, depends on T, solvent

Types of Equilibrium Constants: Concentration based (K)

Note that ax = x[x] If solutes have small difference between activity and equilibrium concentration for the reaction mA + nB pC + qD

K = (caC)p(DaD)q (AaA)m(BaB)n

Types of Equilibrium Constants: Concentration based (K)

K = (caC)p(DaD)q (AaA)m(BaB)n K = [C]p[D]q . [c]p[D]q [A]m[]n [A]m[B]n K = K . [c]p[D]q [A]m[B]n

Types of Equilibrium Constants:

Note: at infinite dilution, K K most calculations use K instead of K; molarities as approximations of activities since x difficult to calculate due to numerous unknown parameters