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# 1/20/2015

Acid-Base Equilibria and
Neutralization Methods
Acid-Base Equilibria
and
Neutralization Methods

Review units of concentration (calculations)
Acid Base theory
Relative strength of acids and bases
Chemical equilibrium
Electrolyte effects on chemical equilibria
Distribution of acid base as a function of pH
Systematic method of equilibrium calculation
– PBE, MBE, CBE
– Calculation of pH

Buffer solutions
Acid base titrations/Applications

REVIEW: Units of Concentration

REVIEW: Units of Concentration
concentrat ion 

amount of solute
amount of solution

Molarity

(M)

- also called Equilibrium,
or Species Molarity

M=

moles solute
liters of solution

Analytical and Equilibrium Concentrations
Equilibrium Molarity, [X] = concentration of a given
dissolved form of the substance
Analytical Molarity, Cx = sum of all species of the
substance in solution

Formality (F) or Analytical molarity
F=

REVIEW: Units of Concentration

Example:
What is the concentration (M and F) of a
solution prepared by dissolving exactly 1
mol of acetic acid in 1 liter of solution?
(The acid is 0.42% ionized)

moles solute
liter of solution

REVIEW: Units of Concentration

Normality (N)
N

=

# of equivalents of solute
liter of solution

Molality (m) - defined as the number of
moles of a substance per kilogram of solvent
(not solution)
m=

moles of solute
kg of solvent

1

1/20/2015

REVIEW: Units of Concentration

REVIEW: Units of Concentration
Parts per thousand:

TRY THIS!
Calculate the N, m and F of 5.700g H 2SO4 in
1L solution (H2SO4=98.08 g/mole)

Show relationship between N and M.

REVIEW: Units of Concentration
Percent concentration (or parts per hundred)

• Weight percent (w/w):
C(w/w) = weight solute x 100%
weight solution

Cppt = weight of substance x 1000
weight of solution
Parts per million (ppm) or parts per billion (ppb)
Cppm = weight of substance
weight of solution

x 106

Cppb = weight of substance
weight of solution

x 109

REVIEW: Units of Concentration
Density and Specific Gravity
A. Density = mass/volume
B. Specific Gravity = Density of substance
Density of water

• Volume percent (v/v):
C(v/v) = volume solute x 100%
volume solution
Indicate

the unit!!!

• Weight/Volume percent (w/v):
C(w/v) = weight solute(g) x 100%
volume solution(mL)

Sample Calculations:
a.Calculate the molar concentration
and molality of commercially available
concentrated acids and bases below:
Reagent
CH3COOH
NH3
HCl
HF
HNO3
HClO4
H3PO4
H2SO4

%w/w

Specific gravity

99.7
29.0
37.2
49.5
70.5
71
86
96.5

1.05
0.90
1.19
1.15
1.42
1.67
1.71
1.84

PREPARATION OF SOLUTION
Describe the preparation of the following
solution
a. 2.00 L of 0.150 M HClO4 from a 12.0 M
HClO4
b. 2.00 L of 0.150 M HClO4 from a
concentrated solution that has a specific
gravity of 1.66%
c. 100 mL of 0.1500 M of Na2SO4 from
Na2SO4 crystals.
d. 250.0 ml of 100.0 ppm of Na from Na2SO4
crystals.

2

1/20/2015

ACID BASE THEORY

Bronsted and Lowry

Arrhenius theory - Svante Arrenhius
(1857-1927)
Acids – a substance that increases the
concentration of H3O+ when added to water
Bases - a substance that decreases the
concentration of H3O+ when added to H2O
or produces OH-

Acids – proton donors
Bases- proton acceptors
The Bronsted and Lowry definition does not
require that H3O+ be formed

Bronsted and Lowry
A Brønsted–Lowry acid…
…must have a removable (acidic) proton.
HCl, H2O, H2SO4

Bronsted and Lowry
A Brønsted–Lowry base…
…must have a pair of nonbonding electrons.
NH3, H2O

Fundamental ideas from Bronsted and Lowry

Assignment:
Samples of Bronsted and Lowry acid
and base but not Arrhenius

1. Amphiprotic species (or amphoteric)
– species that have both acidic and basic properties

3

• Atoms with an empty valence orbital can be Lewis acids. Substances with negligible acidity do not dissociate in water. • Anything that is a Brønsted–Lowry base is also a Lewis base. • A compound with no H’s can be a Lewis acid. Autoionization OH- Lewis Acid-Base Concept Lewis Acids • electron-pair acceptors. meaning “to join together.dissociates only slightly when it dissolves in water .1/20/2015 Fundamental ideas from Bronsted and Lowry Practice: Determine the conjugate acid base pair 2. .Their conjugate bases are weak bases. Conjugate Acids and Bases: • From the Latin word conjugare. Fundamental ideas from Bronsted and Lowry 3.” • Reactions between acids and bases always yield their conjugate bases and acids. 4 .Their conjugate bases are quite weak.dissociates more or less completely when it dissolves in water. Weak acid . Their conjugate bases are exceedingly strong. Lewis Acid-Base Concept Lewis Bases STRENGTH OF ACIDS AND BASES Strong acid . • electron-pair donors.

1/20/2015 STRENGTH OF ACIDS AND BASES STRENGTH OF ACIDS AND BASES In any acid-base reaction. HBr are all strong acid STRENGTH OF ACIDS AND BASES Leveling solvent – two or more acids give the same acid strength – one in which all acids are dissociated to the same degree and have equal acid or base strength Example: HCl(aq) + H2O(l)  H3O+(aq) + Cl–(aq) HClO4(aq) + H2O(l)  H3O+(aq) + HClO4. e. so the equilibrium favors the backward reaction (K<1). Acetate is a stronger base than H2O. Which is a stronger acid HCl or HClO4? HClO4 + HAc  H2Ac+ + ClO4+ HCl + HAc  H2Ac + ClHClO4 dissociate 5000 times greater in Hac than HCl p. HCl(aq) + H2O(l)  H3O+(aq) + Cl–(aq) acid base c.log H+ pOH =.log OHpKw = . base H3O+(aq) + C2H3O2–(aq) HC2H3O2(aq) + H2O STRENGTH OF ACIDS AND BASES Assign: Explain why HF behave as a weak acid while HI. HCl. acid The stronger base “wins” the proton.is a measure of the acidity or alkalinity of a substance Assign: Show that: pH + pOH = 14 5 . c. the equilibrium favors the reaction that moves the proton to the stronger base.log Kw pH .Functions The negative logarithmn (to the base 10) of the number pX = -log X pH = .g.(aq) STRENGTH OF ACIDS AND BASES Differentiating solvent – allows relative strength to be measured — a solvent where various acids dissociate to different degrees and have different strengths.

Dissociation constant of water – Kw 2. water. Dissociation constant of water .Ka 3. A pure solid.  The equilibrium. molar concentration of a solute  The partial pressure (in atmospheres) for a gas.0    Practice : • Calculate pH of pure water at 25°C and 50°C.. Ionization constant for acid . 10-14 6 . o o o o pH = 2.Kw K equil  [ H 3O  ][OH  ] K equil [ H 2O ]2  [ H 3O  ][OH  ] [ H 2O ]2    K w  H 3O OH At 25°C. Example: CHEMICAL EQUILIBRIUM Le Châtelier’s Principle When a stress is imposed on a system at equilibrium the system will respond in such a way as to relieve the stress. CHEMICAL EQUILIBRIUM Types of equilibria 1. Kw = 1. Ionization constant for base . Addition of a reactant Change in pressure or volume of a gas Change in temperature + dD C  D   A B  D A B "[ ]" means.Kb CHEMICAL EQUILIBRIUM Types of equilibria 1.1/20/2015 Significant figure in pH calculations: The number of digits in the mantissa would be the number of significant digits in x of log x. CHEMICAL EQUILIBRIUM aA + bB Or Keq  The number of significant figure in the x of log x would be the number of digits in the mantissa.00347 cC C A pure liquid in excess. The solvent.  Is assumed to be "1" if the species is.460 [H+] = 0.. The solvent in a dilute solution.

1/20/2015 Ionization constant for acid .Ka Types of equilibria The greater the value of Ka. 2. the stronger the acid. Ionization constant for base .Ka Ka  [ H 3O  ][ Ac  ] [ HAc ] Ka can be used to distinguish between strong acids and weak acids. derive relationship between each of two acids and their conjugate base 7 . Types of equilibria 3.base pair HAc + H2O Ac- Ac.+ H2O Ka  [ H 3O  ][ Ac  ] [ HAc ] + HAc + Kb  H3O+ OH[ HAc ][OH  ] [ Ac  ] Show that: Kw= kakb Practice: What is the Kb for the equilibrium where Ka is 6.Kb NH3 + H2O Kb  NH4+ + H3O+ [ NH 4  ][ H 3O  ] [ NH 3] Assignment: Why is it that H2O does not appear in equilibrium constant expression for aqueous solutions? Relationship between Ka and Kb for conjugate acid . Ionization constant for acid .2 X 10-10 CN.+ H2O HCN + OH- Assign: For a diprotic acid.

At 1 x 10-2 M NaCl. 2. Calculate the ionic strength (µ) of 0. 3. Calculate the ionic strength (µ) of a 0. Electrolyte Effects Consider the effect of added NaCl to increase the size of the Ksp for barium sulfate: 1. B .020 M KBr plus 0. The electrolyte effect is dependent upon its ionic strength.1 M NaNO3 solution.8 x 10-10. Ksp ≈ 1. Ksp ≈ 2. ZC .7 x 10-5.1 M Mg(NO3)2 solution.010 M Na2SO4 8 . Ka ≈ 2.µ Ionic strength. Real Solutions Constants vary based on electrolyte concentration. Ionic strength. C  are the molar concentrations of each ionic species and ZA.. Ka = 1.µ . This results in deviation from ideal behavior.85 x 10-10. Ka ≈ 2. At 1 x 10-1 M NaCl. ZB.1/20/2015 ELECTROLYTE EFFECTS aA + ELECTROLYTE EFFECTS ON CHEMICAL EQUILIBRIA bB cC Keq '  + dD C C D D  AA B B Ideal Solutions Equilibrium constants are independent of the presence and concentration of electrolytes. At 0 M NaCl.. At 1 x 10-3 M NaCl. Ksp = 1.1 x 10-5.75 x 10-5. At 0 M NaCl. 2..1 x 10-10. Electrolyte Effects Consider the effect of added NaCl to increase the size of the Ka for acetic acid: 1.a measure of the total concentration of ions in solution  1 AZ A2  BZ B 2  C Z C 2   2  A. 3. are the charges on each species Sample calculation: Calculate the ionic strength (µ) of a 0. At 1 x 10-2 M NaCl.

01. 0. then the equation becomes • . aX   X X  Activity and Activity Coefficients The activity coefficient Activity. u 1  3. is the "effective" concentration of a chemical species.3x  The constants 0. for ions with higher charge. µ The higher the charge in the ionic atmosphere the greater the ionic strength of a solution.permits the calculation of activity coefficients of ion from their charge and their average size.512 Z 2 X  This equation is referred to as the Debye Huckel Limiting Law (DHLL) DHLL can be used to calculate/approximate activity coefficients in solutions of very low ionic strength.512 Z 2 X  9 . Where: X [X] = molar conc’n of species X = activity coefficient Activity and Activity Coefficients X Debye-Huckel equation • Dimensionless factor that measure the deviation of behavior from ideality.1/20/2015 Activity and Activity Coefficients Ionic strength.3 are applicable to aqueous solutions at 25 oC The value of  is approximately 0.ax .3x  Zx = charge of the ion x µ = ionic strength αx = effective diameter of the hydrated ion in nanometers u  log  x  0. • Assumed to be "1" for uncharged molecules.Term used to account for the effects of electrolytes on chemical equilibria.512 Z X  1  3.  may be as large as 1.  log  x  0.512 Z X  2  log  x  where 2 Debye-Huckel equation . The stoichiometry of the electrolyte determines the ionic strength.3 nm for most singly charged ions. is the numerical factor necessary to convert the molar concentration of the chemical species to activity.0 nm when   0.Na2SO4 Al(NO3)3 MgSO4 Ionic strength C 3C 6C 4C Activity coefficient. • Calculation of Activity Coefficients – Debye-Huckel Equation – Extended Debye-Huckel equation – Davies equation  log  x  0. Type of electrolyte 1:1 1:2 or 2:1 1:3 or 3:1 2:2 Example Compound NaCl MgCl2. ɣx .51 and 3.

5 nm For the general equilibrium • aA + bB Concentration Equilibrium Constant Thermodynamic Equilibrium Constant cC + Since: dD [C ]c [ D ]d Keq '  [ A]a [ B ]b Keq  aC a D c d a b a A aB aX   X X  Then:  C C   D D  A B  A  A   B B  C Keq  Keq  Keq  D c d a b a A aB  C D C  D  A B  A B  A B  C  aC a D D  C D Keq '  A B DISTRIBUTION OF ACID BASE AS A FUNCTION OF PH DISTRIBUTION OF ACID BASE AS A FUNCTION OF PH Objective: • To find an expression for the fraction of an acids and bases (α) as a function of pH. α = 0.1/20/2015 Activity and Activity Coefficients Activity and Activity Coefficients Sample calculation: Calculate the activity coefficient for Hg2+ in a solution that has an ionic strength of 0.085. • An α fraction is the ratio of the equilibrium concentration of one specific form of a solute divided by the total concentration of all forms of that solute in an equilibrium mixture. 10 .

8 x 10-5 HAc (aq) + H2O H+ (aq) + Ac– (aq) DISTRIBUTION OF ACID BASE AS A FUNCTION OF PH • αo= the fraction of HAc • α1 = the fraction of Aco  MBE: CHAc= [HAc ] + [Ac-] PBE: c [H+ ] = [OH.1/20/2015 DISTRIBUTION OF ACID BASE AS A FUNCTION OF PH Monoprotic system • Consider 0.10 M HAc Ka = 1.] + [Ac-] Ka  1  [ H  ][ Ac  ] [ HAc ] DISTRIBUTION OF ACID BASE AS A FUNCTION OF PH Rearranging Ka to get HAc  and [ Ac  ] Ka  [ Ac  ]  Ka [ HAc ] [H  ] [ H  ][ Ac  ] [ HAc ] [ HAc ]  • Substituting the above equations into αo expression Ka [ HAc ] [ HAc ] [ Ac  ]  o   [H  ] [ HAc ]  [ Ac ] [ H  ][ Ac  ] Ka • Substituting the above equations into α1 expression [ Ac  ] [ HAc ]  [ Ac  ] [ HAc ]  [ H  ][ Ac  ] Ka [ Ac  ] [ Ac  ]   [ HAc ]  [ Ac ] c HA DISTRIBUTION OF ACID BASE AS A FUNCTION OF PH o  DISTRIBUTION OF ACID BASE AS A FUNCTION OF PH 1  [ HAc ] [ HAc ]  [ HAc ]  [ Ac  ] C HA [ HAc ] [H  ]   c HA [H ]  K a DISTRIBUTION OF ACID BASE AS A FUNCTION OF PH When: [HAc] = [Ac-]  o  1 Assign: Derive this Ka = [H+] pKa = pH 11 .

Kn 12 .1/20/2015 DISTRIBUTION OF ACID BASE AS A FUNCTION OF PH • Plot of the fraction of Ac.45 x 10-7 Ka2=4.present in each of the 2 forms as a function of pH. at pH 6. at pH 2.5 and pH 12 4.9×10–10 HCN + H2O CN– + H3O+ 1. At what pH will [HCN]=[CN-] Distribution diagram: Carbonate system Ka1=4. Draw the distribution diagram 2.5 of HCN and CN3. at pH 4.20 M HCN Ka = 4.00 2. CH3COOH (aq) H+ + CH3COO– (aq) Example: Calculate α values: 1.74 3. Calculate the concentration at pH 3.50 Distribution Diagram Practice: 0. + K1K2K3…. What species will predominate at pH 2.45 x 10-11 Distribution Diagram Derivation of  Expressions for Polyprotic Weak Acids For H2CO3 fraction of H2CO3 fraction of HCO3- fraction of CO32- o  [ H  ]2 [ H  ]2  [ H  ]K a1  K a1 K a 2 1  [ H  ] K a1 [ H  ]2  [ H  ]K a1  K a1 K a 2 2  K a1 K a 2 [ H ]  [ H  ] K a1  K a1 K a 2  2 General form for the polyprotic acid HnA  Hn H  A  D K a1 H    H n1 A  D Where D = [H+]n + K1[H+]n-1 + K1K2[H+]n-2 + ….

H3A 0.).1/20/2015 Assignment: • Derive the alpha expressions for all PO4bearing species in a phosphoric acid or phosphate solution.10 F H2SO4 0.20 F Na2S 0.20 F Na2H2Y 13 . H2A.50 M H2CO3 NaHCO3 Na2CO3 H3PO4 Sat’d solution of Ag3PO4 SYSTEMATIC METHOD OF EQUILIBRIUM CALCULATION Mass balance equations (MBE ) Equations that relate the equilibrium concentrations of species in a solution to each other and the formal (analytical) concentrations of the solutes. Mass-balance equations (MBE) Charge-balance equations (PBE) Proton Balance equations (PBE) Mass balance equations (MBE ) Example: Write a mass balance expressions for the ff: a) b) c) d) e) f) g) h) HA.10 F NH4Cl 0. etc.50 M HCN 0. Equilibrium constant expressions (Ka. Ksp. Draw the distribution diagram SYSTEMATIC METHOD OF EQUILIBRIUM CALCULATION Four types of algebraic expressions commonly derived/used in solving multiple equilibria. Kf. It states that C  HA  A  .  HA Mass balance equations (MBE ) ASSIGN: Write the MBE for the following solutions: 1) 2) 3) 4) 0. that is analytical concentration of an acid or base is equal to the sum of concentrations of the protonated and unprotonated species. Kb.50 M CH3COOH 0.

Na3PO4 NH3 CH3COONa • PBE for polyprotic acids and bases H2 S NaHS Na2S Charge Balance Equation (CBE) Equations that express the electrical neutrality of a solution by equating the molar concentrations of the positive and negative charges.KCN Proton Balance Equation (PBE) Try this: Write a proton balance expression for the following: ASSIGN: Write PBE for the following acids and bases: • PBE for weak base(monobasic) 1.HBr strong base . Charge Balance Equation (CBE) Example: Write CBE for 0.1/20/2015 Proton Balance Equation (PBE) Proton Balance Equation (PBE) Matches the concentration of species which have released protons with those which have consumed. H3PO4 4.HCN weak base(monobasic) NH3 Salt . NaH2PO4 6. Na2CO3 3. Na2H2Y H3O+(aq) + CO32-(aq) OH-(aq) + H2CO3(aq) H3O+(aq) + OH-(aq) 14 .1 M solution of NaHCO3 Na+(aq) + HCO3-(aq) (1) NaHCO3(s) (2) HCO3-(aq) + H2O(l) HCO3-(aq) + H2O(l) (3) 2H2O(l) sum (+) charge = sum (-) charge Neutral species are not included 5. # protons consumed = # protons released proton rich = proton poor Practice: Write a proton balance expression for the following: proton rich = proton poor a) b) c) d) e) f) H 2O strong acid . Na2HPO4 7.KOH weak acid(monoprotic) . H2CO3 2.

a solution is possible. you must either find more equilibria or else a solution is not possible. Steps in solving problems of multiple equilibria Make suitable approximations to simplify the algebra.50 M =[HX] + [X-] CBE: [H+] = [OH-] + [X-] Strong acids and bases Write out all equilibrium constants and obtain their values Kw = 1. Solve the algebraic equations.0 x 10-14 = [H+] [OH-] Count the number of species [H+] [OH-] [X-] [HA] Count the number of independent algebraic relationships PBE. CBE. HX 2. Check the validity of the approximation. If the number of independent equations < the number of unknowns.1/20/2015 Steps in solving problems of multiple equilibria TRY THIS! Write the charge balance expression Write balanced reactions for all equilibria. Kw  solution is possible 15 . CBE) Write out all equilibrium constants and obtain their values 1) HBr 2) Na2HPO4 3) H3PO4 Steps in solving problems of multiple equilibria Count the number of unknown species in the equilibrium system and count the number of independent algebraic relationships available in the MBE. MBE. and Keq expressions. CBE) PBE: [H+] = [OH-] + [X-] MBE: 0. If the number of independent equations > the number of unknowns. Calculation of pH Strong acids and bases Calculate the pH of 0. MBE. Write all equations (PBE. H2O H+ + H+ X+ OH- Write all equations (PBE.50 M HX Write balanced reactions 1. MBE.

Kw  Solvable 1.) 0. Most of the acid HA remains in the undissociated form such that [HA] >>[A-] MBE: CHA = 0.0 x 10-14 = [H+] [OH-] Ka  Weak acids and bases H A  Weak acids and bases Make suitable approximations to simplify the algebra Two assumptions to remove the unknown terms:   HA Count the number of species: [H+] [OH-] [A-] and [HA] Count the number of independent algebraic relationships: PBE.50 M = [HA] + [A-] 16 .) 0.025 M KOH b.50 M) Write balanced reactions 1. MBE. Most of the H+ come from the dissociation of the acid and contribution from water is negligible.50 M = [HA] + [A-] CBE: [H+] = [OH-] + [A-] pH   log C HX Weak acids and bases Write out all equilibrium constants and obtain their values Kw = 1. Calculate pH a. PBE: [H+] = [OH-] + [A-] 2.0 x 10-6 M HCl Strong acids and bases General formula for strong acid would be: H    C HX  C HX  4Kw 2 This formula is applicable for strong acid with concentration HX   10 6 M 6 For strong acid with HX   10 M H   X   C   Then HX Consider a weak acid HA (0.0 x 10-8 M KOH d. H2O H + OH Write all equations (PBE. MBE. CBE) PBE: [H+] = [OH-] + [A-] MBE: CHA = 0.) 1.15 M Ba(OH)2 c.1/20/2015 Strong acids and bases Strong acids and bases Make suitable approximations to simplify the algebra Solve the algebraic equations Check the validity of the approximation. HA H+ + A+ 2.) 1.

we can assume that [OH-] is very small PBE [H+] = [OH-] + [CH3COO-] [H+] = [OH-] + [CH3COO-] MBE 0.10 = [CH3COOH] + [CH3COO-] Ka  PBE [CH 3COO  ][H  ] [CH 3COOH ] K w  [H  ][OH  ] pH Calculations K a  1.[H+] = [CH3COOH] Exercise Calculate the pH of 0.10  [H  ] assume that [H+] is negligible 17 .10 M CH3COOH. approximations are used to solve for the unknown  Using the quadratic equation [H  ]  1.10 .[CH3COO-] = [CH3COOH] 0. Ka = 1.10  [H  ]  0  [H ]  Ka[H ]  0.10 = [CH3COOH] + [CH3COO-] Method of Successive Approximations  Substituting and simplifying equations   MBE can be rewritten as K a  1.88 0. CH3COOH.8 x 10-5  Steps are the same  For the last step. Ka = 1.1/20/2015 pH Calculations Weak acids and bases Substituting this to Ka expression H A    Ka   HA  H   2 H H    H  Exercise Calculate the pH of 0.10 .33  10 3 M pH  2.8  10  5  [H  ][H  ] 0.10 M CH3COOH. pH Calculations pH Calculations  4 independent equations  Since the solution is acidic. OH-.8 x 10-5  2  C HA C HA  pertinent equilibria CH3COOH  H+ + CH3COOH2O  H+ + OH-  KaC HA H   KaC HA 4 species: H+. CH3COO- Check the validity of the approximation.8  10  5   2  [H ][H ] 0.10 Ka 0.

0  10 7 M 18 .0  10  7  [OH  ]II 5. then solve for [H+]II K a  1.10  [H  ]  Iterations have converged [H  ]V  1.34  10  3 [H  ]II  1.2  10  7 M [OH  ]I  FNaOH  5.1/20/2015 Method of Successive Approximations Method of Successive Approximations [H  ]I  K a  0. OH-.33  10 3 M  [H ][H ] 0.33  10 3 M [H  ]IV  1.33  10 3 M Method of Successive Approximations Exercise Calculate the pH of 5.8  10 5 )(0.0  10 14  5.8  10  5  [H  ]III  1.10  (1.0 x 10 -7 M NaOH solution Method of Successive Approximations  3 independent equations PBE [H+] + [Na+] = [OH-]  pertinent equilibria NaOH  Na+ + OHH2O  H+ + OH- MBE FNaOH  5.34  10 3 M  Substitute the answer to the Ka expression.10)  1. Na+ Method of Successive Approximations [H  ]  Kw [OH  ] Method of Successive Approximations  Substituting and simplifying equations Kw  FNaOH  [OH  ] [OH  ]  Assume water has very small contribution in [OH -] Kw  FNaOH  [OH  ] [OH  ] Kw  FNaOH  [OH  ]II [OH  ]I 1.8  10  5  K a  1.10  1.33  10 3 M [H  ][H  ] 0.0  10  7 [OH  ]II  5.0  10 7 M  [Na  ] [H+] may be derived from the Kw expression 3 species: H+.

diprotic acids H2B + H2O  H3O+ + HB- K a1  [H3O  ][HB  ] [H 2 B ] HB.358 x 10-10). Ka2 = 1.0  10  7  [OH  ]III 5.1/20/2015 Method of Successive Approximations pH Calculations pH of Polyprotic Acids/Bases Kw  FNaOH  [OH  ]III [OH  ]II 1.+ H3O+ K a2  [L ][H3O  ] [HL ] 2H2O  H3O+ + OH- K w  [H3O  ][OH  ]  Assume that any solution containing an appreciable quantity of H2L+ will contain essentially no L.0  10 14  5.487 x 10-3.have 93  10  8 M converged  V 7 pH  7.19  10  7 M [OH  ]  5.72 [OH ]  5.19  10 M [H  ]  1.+ H2O  H3O+ + B2- K a2  [H3O  ][B 2  ] [HB  ] pH Calculations pH Calculations Example Alanine Hydrochloride is a salt consisting of the diprotic weak acid H2L+ and Cl-.10 M H2L+ solution (Ka1 = 4. Calculate the pH of 0. pH of Polyprotic Acids/Bases  Usually Ka1  Ka2 K a1 Ka1  H3O+ from neutral species Ka2  H3O+ from a charged species H2L+ pH Calculations  K b2 K a2 HL  K b1 L- pH Calculations  pertinent equilibria H2L+ + H2O  HL + H3O+ K a1  [HL ][H3O  ] [H2L ] HL + H2O  L.2  10  7 [OH  ]III  5.19  10 M  H2B .19  10 7 M  IV 7 Iterations [OH ]  5.(Since Ka1  Ka2) PBE [H3O+] = [OH-] + [HL] MBE CH  2L  [ H 2 L ]  [ HL ] 19 .

 pertinent equilibria HL + H2O  L.358  10 10 K b2  Kw 1. [HL ][H3O  ] [H2L ] pH Calculations  Assume that any solution containing an appreciable quantity of L.487 x 10-3. Ka2 = 1. Ka2 = 1.358 x 10-10).+ H3O+ K a2  [L ][H3O  ] [HL ] HL + H2O  H2L+ + OH- K b2  K w [H2L ][OH  ]  K a1 [HL ] 2H2O  H3O+ + OH- K w  [H3O  ][OH  ] 20 .1/20/2015 pH Calculations pH Calculations  Substituting and simplifying equations  Since H2L+ is a weak acid PBE K a1  [H3O+] = [OH-] + [HL] K a1  MBE CH  2L  [ H 2 L ]  [ HL ] [ H 2 L ]  C H [ H 2 L ]  C H  2L  2L  [ HL ]  Solving the quadratic equation or using MSA [H3O  ]  1.will contain essentially no H2L+ (Since Kb1  Kb2) PBE MBE [H3O+] + [HL] = [OH-] FL  [L ]  [HL ] [L ]  FL  [HL ] Equilibrium constant expression K b1  [HL ][OH  ] [L ] pH Calculations Example Calculate the pH of 0.487  10  3 K w  [H3O  ][OH  ] OH- pH Calculations  Substituting and simplifying equations K b1  K b1 [HL ][OH  ] [L ] [OH  ]2  FL  [OH  ]  Solving the quadratic equation or using MSA [OH  ]  2.0  10 14  w   7.0  10 14   2.solution (Ka1 = 4.358 x 10-10).364  10  5 K a 2 1.677  10 3 M [H3O  ]  3.72 pH Calculations  pertinent equilibria L- + H2O  HL + OH- K b1 HL + H2O  H2L+ + OH2H2O  H3O+ + K 1.10 M L.91  10 2 M pH  1.43 [ H 3O  ][ H 3O  ] C H L  [ H 3O  ] 2  [ H 3O  ] Example Calculate the pH of 0.736  10 12 M pH  11 .487 x 10-3.229  10 12 K a1 4.10 M HL solution (Ka1 = 4.

10 M HL [H3O  ]  (4.11 K a1K a 2 21 .807  10 7 M pH  6.1/20/2015 pH Calculations CBE [H3O+] + [H2L+] = [OH-] + [L-] MBE FHL = [H2L+] + [HL] + [L-] pH Calculations  Next we solve Kb2 for [H2L+] K b2   Assume that [H2L+] and [L-] are significantly lower than [HL] MBE [H2L ][OH  ] K w  [HL ] K a1 [H2L ]  K w [HL ] [OH  ]K a 1 [H2L ]  [H3O  ]FHL K a1 FHL = [H2L+] + [HL] + [L-] pH Calculations  Next we solve Ka2 for [L-] K a2   Substituting equations into the charge balance equation [L ][H3O  ] [HL ] K [HL ] [L ]  a 2  [ H 3O ]  [L ]  pH Calculations K a 2 FHL [ H 3O  ] CBE [H3O+] + [H2L+] = [OH-] + [L-] [ H 3O  ]   F  1 K w  K a 2FHL  [H3O  ] 1  HL    K [ H a1  3O ]  pH Calculations [H3O  ]2  [ H 3O  ]  K a 2 FHL  K w  FHL     1  K a1  K a 1K a 2 FHL  K a1K w FHL  K a1 [H3O  ]  FHL [H3O  ] Kw K F   a 2 HL K a1 [H3O  ] [H3O  ] pH Calculations  For a solution of 0.487  10 3 )(1.358  10 10 )  7.

6 x 10-8).6 x 10-2.) 0. The amount of base is calculated from the excess added beyond equivalence.04 M CH3NH2 solution (Kb = 4.1/20/2015 pH Calculations Exercise Calculate pH 1.00 mL 0. Preequivalence .[H3O+] = [OH-] Post equivalence . only base is present.) 0. At equivalence: 2.Solution of only strong acid (solution of H3O+) Pre equivalence . before any base is added to the acid sample. 3. If the CHA is greater than 10-6 M. [H3O+] = [OH1-] All the acid is consumed. At equivalence: The acid and base have reacted at the stoichiometric ratio. Ka2 = 6.) 0.1000 M NaOH 1.10 M H2SO3 solution (Ka1 = 1. 2.) 0. the [H3O+]total = CHA + [H3O+]water.42 x 10-5).200 M Na2CO3 Calculations required to establish titration curve Initial .As strong base is added but prior to equivalence. the [H3O+]water can be ignored.10 M H2C2O4 solution (Ka1 = 5. Figure 1: Titration curve of a strong base titrating a strong acid 22 . [H3O+] is consumed 3. Ka2 = 5. CHEM 32 3. Initially.Excess moles of strong acid + limiting moles of strong base (solution of H 3O+) Equivalence Point .2 x 10-2.Excess moles of strong base + limiting moles of strong acid (solution of OH -) Sample problem: Derive a curve for the titration of 50.35 x 10-4) 4.0500M HCl with 0.

HCl HCl + NaOH NaCl NaCl + NaOH TITRANT ADDED 0. 24.00 mL (c)..1000 M NaOH SUMMARY: Region Major constituents 1.200 M KOH(aq) solution Calculate the pH during the titration of 50.00 mL 24.00 mL of 0.00 ml Comments pH OF RESULTING SOLUTION Practice: Fill up the table for the titration of HBr with NaOH SAMPLE: 50. The amount of base is calculated from the excess added beyond equivalence. At eq pt.90 mL 25.0500M HCl with 0. we have assumed that the water contribution to the hydronium ion concentration can be ignored.00 mL of a 0.00 mL 10.00 mL 0. Initial 2. Note that. Beyond equivalence: All the acid is consumed.100 M HBr(aq) solution. 4. only base is present.10-6 M must the water contribution to the hydronium ion concentration be considered • Sample problem: Derive a curve for the titration of 50.00 mL 25. 25. After eq pt. you can also assume that the water is primarily responsible for the hydronium ion concentration. 25. Pre-equivalence 3. Only when the CAcid is between 10-8 .00 ml 40..1/20/2015 4.0500 M NaOH with 0. TITRANT: stepwise addition of a 0. and that the added acid is insignificant.50 mL 23 . If the CAcid < 10-8 M.50 mL (b).10 mL 30. If the CAcid > 10-6 M.1000 M HCl after the addition of the following volumes of reagent (a).

10. become less distinct.00 mL 24. NH4Cl + HCl Comment Titration curve and effect of concentration and Ka As the acid becomes dilute the EP become shorter.00 mL 10.1000 M HCl. Before E.P. At E.200 M KOH(aq) solution titrant added region classification 0.00 (c).10 mL 30.00 ml Titration of weak base with a strong acid Titrant: HCl Analyte: NH3 pH of resulting solution Practice: A 50.00 ml 40.100 M HF(aq) solution TITRANT: 0.00 mL 25. After E.00 mL of acid. Initial NH3 2.P.00 mL of a 0.75 x 10-5) with 0. 24 .1000 M NaOH Figure 2: Titration curve of a strong acid titrating a strong base Practice: SAMPLE: 50.00 mL aliquot of 0. Calculate the pH after the addition of (a).00 (b). NH3 + NH4Cl 3.00 mL of 0.0500 M NaCN is titrated with 0. Summary: Region Major constituents 1. the more limited the choice of indicator.90 mL 25.P.00 and (d). 25. NH4Cl 4. 0.1/20/2015 Derive a curve for the titration of 50.1000 M acetic acid(Ka = 1. 26.

At EP1 4. but before the EP2 5. (Ka1 = 1. but before EP1 3.10 M H2CO3 after addition of 0.10 M NaOH.. Try this! Find the pH of a 50 mL solution of a 0. Acid-Base Indicators Acid-Base Indicators • For a typical indicator In   10 we can see the In. 75. Titrant added. At EP2 6. Ka2 = 1.00 x 10-8) TITRATING POLYFUNCTIONAL ACIDS AND BASES Acid-Base Indicators Acid-base indicators (pH indicators) are weak organic acids or weak organic bases that change color as a function of ionization state. After EP1.8x10-11 Act as a second acid or base in the solution being titrated and must be weaker than the analyte so that it reacts last with the titrant. 2. Initial .1/20/2015 TITRATING POLYFUNCTIONAL ACIDS AND BASES Regions: 1. After EP2 TITRATING POLYFUNCTIONAL ACIDS AND BASES Sample problem Consider 20.00 x 10-4.color.3x10-7 and ka2 = 4. titrated with 0.100 M NaOH.No titrant added.00mL of 0. Ka1=4.100 M H2A. In   10 we can see the HIn color  HIn  H O In   Ka  3  HIn  H O   Ka HIn  In    3  HIn  In   pH  pKa  log HIn  25 . and 150 mL of 0.. 25. 100. 50.

3 7.0 4.0-9.1 6.8 9.4 5.2 3.8-6.9-4.5 acid form Acid-Base Indicators Selecting the Proper indicator • The transition range of the indicator should overlap the steepest part of the transition curve.00100 M NaOH base form Acid-Base Indicators Titration curves for HCl with NaOH A: 50.9 9.0 4.100 M NaOH B: 50.001000 M HAc with 0.0 4.00 mL 0.2 6.3-10.6 8.7 8.00 mL of 0.3 2. Indicator range = pKa ± 1 Acid-Base Indicators • Titration curves for HAc with NaOH A: 0.1000 M HAc with 0.00100 M NaOH Acid-Base Indicators Indicator Error Determinate error difference between the endpoint and the equivalence point pH at which the indicator completes its color change is not the same as the pH of the EP Indeterminate error inability to decide if its end point or not 26 .000500 M HCl with 0.2-6.0-7.1-4.4-9.1/20/2015 Acid-Base Indicators Selected pH indicators Common name Methyl yellow Methyl orange Methyl red Chlorophenol red Bromthymol Blue Cresol Purple Phenolhpthalein Thymolphthalein Acid-Base Indicators • Ex.0500 M HCl with 0.0 9.1000 M NaOH B: 0.4 7. Phenolhpthalein (phe) pKa Indicator Range 3.

assuming the solution is to be used for titrations in which the reaction is Exactly 50.03926 N Ba(OH)2 to give an end point with bromocresol green indicator.3.0-5. the following general reaction exists.99 g/mol) from the primarystandard solid.00 mL of an HCI solution required 29.1000 N Na2CO3 (105.0 – ph 2. phenol red which has a yellow HIn form.71 mL of 0. and a Ka of 5.. acidic endpoint basic bromocresol green yellow green blue 4.6 Indicate the reaction that will take place when – acid is added – base is added What is the pH transition range of the indicator What species and color will predominate in a solution of – pH 8.+ 2H+  H2O + CO2 27 . a red In. CO32.0 Acid-Base Indicators Sample problem 2: Consider the indicator.form.00 L of 0.0 x 10-8. Calculate the normality of the HC!.1/20/2015 Acid-Base Indicators Sample problem 1: For bromcresol green. If a few drops of this indicator are added to a solution of pH 2. What is the ratio of HIn/In. what color would the solution be? APPLICATIONS OF ACID BASE TITRATIONS APPLICATIONS OF ACID BASE TITRATIONS Concept of equivalence (review) Preparation of standard acid solutions Standardization of acids Primary standards for acids Preparation of standard base solutions Standardization of bases Applications of neutralization titrations Elemental analysis Determination of inorganic substances Determination of organic functional groups Concept of equivalence (review) Concept of equivalence (review) Describe the preparation of 5.

+ H2O pH 8. HClO4 HCl – widely used for titration of bases H2SO4 and HClO4 – useful for titrations where chloride ion interferes by forming precipitates HNO3 are seldom used because of their oxidizing properties Na2CO3 – available commercially or can be prepared by heating purified NaHCO3 between 2700C to 3000C for 1 hour 2NaHCO3 Standardization of acids  Na2CO3 + H2O + CO2 Standardization of acids THAM or TRIS . NaOH ) react rapidly with atmospheric CO2 to produce carbonate CO2(g) + 2OH CO32. H2SO4.4916 g of Borax.1/20/2015 Preparation of standard acid solutions Standardization of acids Strong acids are used like HCl.+ H3O+  H2CO3 + H2O pH 3.+ H2O So that this carbonate will also be titrated CO32.+ 2H3O+  H2CO3 + 2H2O But no error is incurred because it cancels out by the OH.+ H3O+  HCO3.8 H2CO3  CO2 + H2O Standardization of acids Preparation of standard base solutions Effect of CO2 absorption sodium tetraborate .65 mL of HCl were used to titrate 0. 27.consumed 28 .Na2B4O7 • Ex.g.tris-hyhydroxymethyl)aminomethane (HOCH3)CNH2 Na2CO3 CO32. Molarity of HCl is: Bases (e.3 HCO3.

NaOH But if an indicator in the basic transition range is used then each CO32 reacted with only one hydronium ion when the color change is observed CO32. Titration Nitrogen sulfur Determination of inorganic substances ammonium salts nitrates and nitrites carbonate and carbonate mixtures Determination of organic functional groups Determination of salts Kjeldahl Method for Determining Nitrogen Digestion in strong sulfuric acid in the presence of a catalyst Sample + H2SO4 → (NH4)2SO4(aq) + CO2(g) + SO2(g) + H2O(g) Conversion of ammonium ions into ammonia gas.+ 2H2O The effective concentration of the base is thus diminished by absorption of CO2.g. Distillation 3. heated and then distilled. and a systematic error (called a carbonate error) results. Kjeldahl Method for Determining Nitrogen Titration back titration .+ 2H3O+  HCO3. KHC8H4O4 Benzoic acid Potassium hydrogen iodate. Standardization of bases Primary standards: Potassium Hydrogen Phthalate. KH(IO3)2 Applications of neutralization titrations Kjeldahl Method for Determining Nitrogen Elemental analysis 1.the ammonia is captured by a carefully measured excess of a standardized acid solution in the receiving flask Receiver: 2NH3 + 2H2SO4 → (NH4)2SO4 + H2SO4 Titration: H2SO4 + 2NaOH → Na2SO4 + 2H2O (NH4)2SO4 + 2NaOH → 2NH3 + Na2SO4 + 2H2O 29 . Digestion 2.1/20/2015 Preparation of standard base solutions Preparation of standard base solutions Effect of CO2 absorption e.

Calculate the percent protein in the flour.00 mL of 0. The excess HCl was then back-titrated with 3.97 mL of 0.7121 g sample of wheat flour was analyzed by the kjeldahl method.1/20/2015 Kjeldahl Method for Determining Nitrogen Kjeldahl Method for Determining Nitrogen • direct titration Sample problem: A 0.04012 M NaOH.04977 M HCl. The ammonia formed by addition of concentrated base after digestion withH2SO4 was distilled into 25. Kjeldahl Method for Determining Nitrogen Kjeldahl Method for Determining Nitrogen DOUBLE INDICATOR DOUBLE INDICATOR Titration curves for NaOH Titration curves for NaHCO3 Titration curves for Na2CO3 30 .

Wht is the percentage composition of the sample? Sample problem: Sample problem: • An impure mixture that may contain NaOH. A second 0. CO32–. With phenolphthalein as indicator. requiring 16.0-mL sample to a pH of 8. and (b) the % composition of each of the component(s) that are(is) present. Na2CO3. The alkalinity of natural waters is usually controlled by OH–. requiring 48.3 requires 18.12 mL of the same titrant to reach a pH of 4.15 mL.00 mL of the acid.00 mL of the acid.17 mL.000 g of this sample was dissolved in 30.67 mL of a 0. and/or NaHCO3 with other inert matter was analyzed. and HCO3–.5000 N HCl.02812 M solution of HCl. the solution turns colorless after the addition of 15.1042 N NaOH. Determine (a) the component(s) present from the three listed.5000 g of this sample was titrated to the phenolphthalein endpoint with 0.5. Methyl orange is then added. Identify the sources of alkalinity and their oncentrations in parts per million. 1. Wht is the percentage composition of the sample? 31 .200 g sample of mixture containing NaHCO3 and Na2CO3 was dissolved and titrated with 0. Titrating a 100. A second 100. requiring 21. A second 1.00 mL more of the acid is required to reach the endpoint. the solution turns colorless after the addition of 30.00 mL more of the acid is required to reach the endpoint. and 5.5000 g sample was titrated to the modified methyl orange endpoint.00 mL more of the acid is required to reach the endpoint. • A 1.200 g sample of mixture containing NaOH and Na2CO3 was dissolved and titrated with 0. and 5.000 g g sample was titrated to the methyl orange endpoint. which may be present singularly or in combination. Wht is the percentage composition of the sample? • A 1. Determine (a) the component(s) present from the three listed. Sample problem: Sample problem: • A 1. Na2CO3. and 22. and (b) the % composition of each of the component(s) that are(is) present. requiring 16.5000 N HCl. and/or NaHCO3 with other inert matter was analyzed. Methyl orange is then added.33 mL. 0. With phenolphthalein as indicator.1042 N NaOH.1/20/2015 Sample problem: Sample problem: An impure mixture that may contain NaOH.00 mL dH2O and titrated to the phenolphthalein endpoint with 0.200 g sample of mixture containing NaOH and Na2CO3 was dissolved and titrated with 0. the solution turns colorless after the addition of 30.33 mL.0-mL aliquot requires 48.5000 N HCl. Methyl orange is then added. With phenolphthalein as indicator.00 mL of the acid.

the solution turns colorless after the addition of 15.33 mL. Na2CO3.200 g sample of mixture containing NaHCO3 and Na2CO3 was dissolved and titrated with 0. and (b) the % composition of each of the component(s) that are(is) present.000 g of this sample was dissolved in 30. and 22.00 mL of the acid. A second 1. and/or NaHCO3 with other inert matter was analyzed.17 mL. Wht is the percentage composition of the sample? • An impure mixture that may contain NaOH.000 g g sample was titrated to the methyl orange endpoint. Methyl orange is then added. requiring 21. With phenolphthalein as indicator.1042 N NaOH.5000 N HCl.1/20/2015 Sample problem: Sample problem: • A 1.00 mL more of the acid is required to reach the endpoint. 1. Determine (a) the component(s) present from the three listed.00 mL dH2O and titrated to the phenolphthalein endpoint with 0. 32 . requiring 16.