Ionic Equilibrium

The Brnsted-Lowry Acid-Base Theory An acid is a proton (H+) donor A base is a proton (H+) acceptor Strong and Weak Acids and Bases

Strength (strong or weak) amount of ionisation / dissociation of a particular acid or base. Concentration amount of acid or base hydrochloric acid (HCl) hydrobromic acid (HBr) hydroiodic acid (HI) nitric acid (HNO3) perchloric acid (HClO4) sulphuric acid (H2SO4)

I) Common strong acids

Example: Hydrogen chloride gas dissociate (break) completely in water. HCl + H2O > Cl- + H3O+

H3O+ ion is hydronium ion All the HCl ionises completely ( 100%) to H3O+ and ClHCl is a strong acid Water acts as a base by accepting the proton from the hydrogen chloride

Calculating ion concentration in solution Example: Initial concentration of HCl 0.15 mol dm-3 = 0.15 moles of HCl gas bubble into a 1 dm3 of water. [HCl] = 0.15 because HCl ionises completely in water. [H3O+] = 0.15 and [Cl-] = 0.15 II) Common strong bases

sodium hydroxide (NaOH) potassium hydroxide (KOH) barium hydroxide (Ba(OH)2) Caesium hydroxide (CsOH) Strontium hydroxide (Sr(OH)2) Calcium hydroxide (Ca(OH)2) Lithium hydroxide (LiOH)

Example: Sodium hydroxide (a salt) dissociates (break) completely in water. NaOH > Na+ + OH

All the NaOH dissociates completely ( 100%) to Na+ + OHNaOH is a strong base Water acts as a acid by donating the proton to sodium hydroxide

Calculating ion concentration in solution Example: Initial concentration of NaOH 0.25 mol dm-3 = 0.25 moles of NaOH into a 1 dm3 of water. [NaOH] = 0.25 because NaOH ionises completely in water. [Na+] = 0.25 and [OH-] = 0.25 III) Common weak acids

ethanoic acid / acetic acid (CH3COOH) fluoroacetic acid (C2H3FO2) formic acid (HCHO2) phosphori(V) acid (H3PO4) boric acid (H3BO3)

Example: Ethanoic acid partially ionises in water. CH3COOH(aq) + H2O(l) <-> CH3COO- + H3O+

About 5% of the ethanoic acid ionises and 95% remains in the molecular form Ethanoic acid is a weak acid Water acts as a base by accepting the proton from the ethanoic acid

Calculating ion concentration in solution Example: Ka expression for the weak acid is Ka = ([H3O+] [CH3COO-]) / [CH3COOH] = 1.8 x 10-5 [CH3COOH] = molar concentration of CH3COOH at equilibrium not initially. [H2O] does not appear in Ka expression because it is a constant. [H3O+] = [CH3COO-] = * CH3COOH ionises partially to form hydronium ion and acetate ion, so the amount of ethanoic acid remaining at equilibrium as the initial amount, 2.0 M, minus the amount that ionises, . * is very small, so that 2.0 is approximately equal to 2.0 = equilibrium concentration of the weak acid with its initial concentration. [CH3COOH] Initial (M) Equilibrium (M) Ka = 1.8 x 10-5 = ([] []) / [2.0] = []2 / [2.0] []2 = (1.8 x 10-5) [2.0] [H3O+] = [CH3COO-] = = 6.0 x 10-3 2.0 2.0 [CH3COO-] 0 2.0 () [H3O+] 0 2.0 ()

IV) Common weak bases

ethylamine (CH3CH2NH2) Ammonium hydroxide / ammonia water (NH4OH)

Ammonia (NH3)

Example: Ammonia partially ionises in water. NH3(g) + H2O(l) <-> NH4+ + OH

About 5% of the ammonia ionises and 95% remains in the molecular form Ammonia is a weak base Water acts as a acid by donating the proton from the ammonia

Calculating ion concentration in solution Example: Kb expression for the weak base is Kb = ([OH-] [NH4+]) / [NH3] = 1.8 x 10-5 [NH3] = molar concentration of NH3 at equilibrium not initially. [H2O] does not appear in Kb expression because it is a constant. [NH4+] = [OH-] = * NH3 ionises partially to form hydroxide ion and ammonium ion, so the amount of ammonia remaining at equilibrium as the initial amount, 2.0 M, minus the amount that ionises, . * is very small, so that 2.0 is approximately equal to 2.0 = equilibrium concentration of the weak base with its initial concentration. [NH3] Initial (M) Equilibrium (M) Kb = 1.8 x 10-5 = ([] []) / [2.0] = []2 / [2.0] []2 = (1.8 x 10-5) [2.0] [OH-] = [NH4+] = = 6.0 x 10-3 2.0 2.0 [NH4+] 0 2.0 () [OH-] 0 2.0 ()

Ostwald Dilution Law Ka = (c)(c) / c(1-) = 2c / (1-) [H3O+] = (Ka x c) Kb = (c)(c) / c(1-) = 2c / (1-) [OH-] = (Kb x c)

Arrhenius Theory: Svante Arrhenius (1884), Sweden

An Arrhenius acid is substances dissociate in water to produce H+ ions An Arrhenius base is substances dissociate in water to produce OH- ions

Example: HCl(aq) > H+(aq) + Cl-(aq) CH3COOH(aq) <-> CH3COO-(aq) + H+(aq)

HCl and CH3COOH are Arrhenius acids

Example: NaOH(aq) > Na+(aq) + OH-(aq) Ba(OH)2(aq) > Ba2+(aq) + 2OH-(aq)

NaOH and Ba(OH)2 are Arrhenius bases

Limitation: Many compound show basic properties but do not contain OHExample: NH3, Na2CO3 and C2H5ONa The Brnsted-Lowry Acid-Base Theory: Johannes Brnsted (1879-1947), Denmark and Thomas Lowry (1874-1936), England

A Brnsted-Lowry acid is a proton (H+) donor A Brnsted-Lowry base is a proton (H+) acceptor In an acid-base reaction, a proton is transferred from an acid to a base

Brnsted-Lowry acid-base reaction: HB(aq) + A-(aq) <-> HA(aq) + B-(aq)

HB and HA act as Brnsted-Lowry acid A- and B- act as Brnsted-Lowry base

Conjugate base is the species formed when a proton is removed from an acid Conjugate acid is the species formed when a proton is added to a base

B- is the conjugate base of HB HA is the conjugate acid of A-

Conjugate acid-base pair differs only in the presence or absence of a proton, H+ Example: Conjugate acid NH4+ HSO4HF Conjugate base NH3 SO42F-

Amphiprotic is a species that can either accept or donate a proton. Example: H2O molecule Hydronium ion (H3O+) H2O molecule gain a proton Hydroxide ion (OH-) H2O molecule lose a proton Lewis Theory: G.N. Lewis (1938), America

A Lewis acid is a species (an atom, ion or molecule) form a dative covalent bond by acceptingan electron-pair from base A Lewis base is a species form a dative covalent bond by donating an unshared electron-pairwith an atom, ion or molecule

Example 1: B(OH)3(aq) + H2O(l) <-> B(OH)4-(aq) + H+(aq)

Lewis acid: Boric acid (H3BO3) Lewis base: Water (H2O)

Example 2: BF3 + NH3 > BF3NH3

Lewis acid: BF3 Lewis base: NH3

Example 3: Cu2+(aq) + 4NH3(aq) > [Cu(NH3)4]2+(aq)

Lewis acid: Cu2+ Lewis base: NH3

Example 4: Ni(s) + 4CO(g) <-> Ni(CO)4(l)

Lewis acid: Ni Lewis base: CO

Water-based Acid-Base Chemistry 2H2O(l) <-> H3O+(aq) + OH-(aq)

water is amphoteric that may act as either an acid or base neutral water naturally dissociates into hydronium and hydroxide only small fraction of water dissociates into solution at 25C (in the absence of an acid or base), water dissociates enough to generate a solution with 10-7M H3O+ and 10-7M OHa neutral aqueous solution, [H3O+ ] = [OH- ] pH = pOH = 7.0

Acid Dissociation HA(aq) + H2O(l) <-> H3O+(aq) + A-(aq)

Ka = acid dissociation constant Ka = ([H3O+ ] [A- ]) / [HA] Each molecule of an acid when added to water, dissociates to form hydronium ion (H3O+) and its conjugate base upon reaction with one water molecule. pKa = -lg Ka Ka = 10-pKa strength of an acid increases (), its Ka () and its pKa () it means that stronger acid have higher Ka values and lower pKa values Ka and pKa of an acid depend on the strength of the acid, but not its concentration

Base Hydrolysis A-(aq) + H2O(l) <-> OH-(aq) + HA(aq)

Kb = base hydrolysis constant Kb = ([OH- ] [HA]) / [A- ] Each molecule of a base when added to water, hydrolyses to form hydroxide ion (OH- ) and its conjugate acid upon reaction with one water molecule. pKb = -lg Kb Kb = 10-pKb strength of a base increases (), its Kb () and its pKb decreases ()

it means that stronger base have higher Kb values and lower pKb values Kb and pKb of a base depend on the strength of the base, but not its concentration Ka pKa Conjugate base strength Kb pKb

Overall Relationship Acid strength

Determination of Reagent Strength pKa(HA) + pKb(A-) = 14

strength of a reagent is determined strictly from Ka (or pKa) and Kb (or pKb) is a measure of the completeness of a reaction in water dissociation = ionisation = electrolytic nature the stronger an acid = the more readily the acid dissociates into water the stronger a base = the more readily the base hydrolysis into water

(*Notes: Not to confuse the concentration of a reactant with its strength (a highly concentrated weak acid may have a lower pH than a strong acid in low concentration.) Strong acids HX(aq) + H2O(l) <-> H3O+(aq) + X-(aq)

strong acids are acids that dissociate fully when mixed with water strong acids ionise completely into hydronium ion and a conjugate base when added to water reactants convert completely into products, so the Ka value of a strong acid is very large the equilibrium constant for the acid dissociation reaction has a large numerator and a minuscule denominator Ka = ([H3O+] [X-]) / [HX] >> 1 pKa < 0 all the strong acids can be classified as either haloacids or oxyacids

Example: Acid HCl HBr HI H2SO4 HNO3 HClO4 Name Hydrochloric acid Hydrobromo acid Hydroiodic acid Sulfuric acid Nitric acid Perchloric acid pKa -7 -7 -9 -9 -2 -10

Weak acids HX(aq) + H2O(l) <-> H3O+(aq) + X-(aq)

weak acids are acids that only dissociate partially when dissolved into water

weak acids do not fully ionize into hydronium ion and conjugate base when added to water Ka = ([H3O+] [X-]) / [HX] where 1 > Ka > 10-14 0 < pKa < 14 Weak acids can be classified in a number of different classification as oxyacids of low oxidation state, one haloacid, carboxylic acids, alkyl ammoniums, and phenol

Example: Acid H2SO3 HClO2 HF HNO2 HCO2H H3CCO2H H2CO3 HClO HBrO NH4+ HCN HIO Name Sulfurous acid Chlorous acid Hydrofluoric acid Nitrous acid Formic acid Acetic acid Carbonic acid Hypochlorous acid Hypobromous acid Ammonium Hydrogen cyanide Hypoiodous acid pKa 1.82 1.90 3.15 3.41 3.74 4.74 6.36 7.46 8.72 9.26 9.32 10.66

Very weak acids HX(aq) + H2O(l) <-> H3O+(aq) + X-(aq)

very weak acid dissociates less than water (Kw = 1.0 x 10-14) Ka = ([H3O+] [X-]) / [HX] where Ka < 10-14 pKa > 14

Strong bases MOH(s) + H2O(l) <-> M+(aq) + OH-(aq)

strong bases react completely when mixed with water strong bases fully hydrolyse water and completely ionize when added water Kb = ([M+ ] [OH- ]) / [MOH] >> 1 pKb < 0 all the strong bases can be classified as either hydrides, hydroxides, alkoxides, amines or carbides

Example: Base Name pKb

LiOH Ba(OH)2 Sr(OH)2

Lithium hydroxide Barium hydroxide Strontium hydroxide

-0.36 -2.02 -2.19

Weak bases A-(aq) + H2O(l) <-> HA(aq) + OH-(aq)

weak bases are bases that only react partially when dissolved into water weak bases partially hydrolyse water weak bases do not fully ionise into when added to water Kb = ([HA] [OH- ]) / [A- ] where 10-14 < Kb < 1 0 < pKb < 14 weak bases are the conjugate bases of the acids common weak bases: carboxylates (RCOO- ), alkyl amines (RNH2), bicarbonate (HCO3- ), carbonate (CO32- ), phosphate (PO43- ) and phonoxides (C6H5O- )

Example: Base BeOH C6H5NH2 NH3 CH3NH2 Zn(OH)2 Ca(OH)2 CsOH KOH NaOH Name Beryllium hydroxide Aniline Ammonia Methylamine Zinc Hydroxide Calcium hydroxide Caesium hydroxide Potassium hydroxide Sodium hydroxide pKb 10.30 9.4 4.75 3.36 3.02 2.37 1.76 0.5 0.2

Very weak bases A-(aq) + H2O(l) <-> HA(aq) + OH-(aq)

very weak bases ionise less than water (Kw = 1.0 x 10-14) Kb = ([HA] [OH- ]) / [A- ] where Kb < 10-14 pKb > 14

Relationship between the strength and the pK scale

strength of the reagent is measured by its ability to react in water strong acids are more readily to dissociated in water (do not confuse the concentration of a reactant with its strength) strong acids have very weak conjugate bases strong bases have very weak conjugate acids

These are some shortnotes for the previous ionic equilibrium studynotes Summary Strong acids / Very weak bases Compound Ka / pKa Conjugate Kb / pKb

Strong acid HCl (pKa = -7) Compound Weak acid RCOOH (pKa = 35) Compound Very weak acid CH4 (pKa = 49)

Ka >> 1 pKa < 0 Ka / pKa 10-14 < Ka < 1 0 < pKa < 14 Ka / pKa Ka < 10-14 pKa > 14

Very weak base Cl(pKb = 21) Conjugate Very weak base RCOO(pKb = 9-11) Conjugate Strong base CH3(pKb = -35)

Kb < 10-14 pKb > 14 Kb / pKb 10-14 < Kb < 1 0 < pKb < 14 Kb / pKb Kb >> 1 pKb < 0

Summary Weak acids / Weak bases

Summary Very weak acids / Strong bases

Ionic product, Kw of water H2O(l) <-> H+(aq) + OH-(aq)

Kc = ([H+] [OH- ]) / [H2O] Kw = [H+] [OH- ] where Kw = Kc [H2O] In pure water at 25C, [H+] = [OH- ] = 10-7 mol dm-3 Ka (acid) x Kb (conjugate base) = 10-14 at 25C pKa + pKb = 14.0 = pKw

pH scale

pH = -lg [H3O+] or pH = -lg [H+] pOH = -lg [OH- ] pH + pOH = 14.0 pH = 14.0 + lg [OH- ] pH = 14.0 pOH

pH values of pure water [H3O+] = 1.0 x 10-7 mol dm-3

pH = -lg [H3O+] or pH = -lg [H+] pH = -lg (1.0 x 10-7) pH = (-7.0) pH = 7.0

pH values of strong acids of 1.0 mol dm-3 (example: HCl)

pH = -lg [H3O+] or pH = -lg [H+] pH = -lg 1.0 = 0.0

pH values of strong bases of 1.0 mol dm-3

pOH = -lg [OH- ] pOH = -lg 1.0 = 0.0 pH = 14.0 pOH pH = 14.0 0.0 = 14.0

pH values of weak acids of 0.15 mol dm-3 (Ka for the acid at 25C is 5.80 x 10-10 mol dm-3) (example: HCN)

for weak acid, [H+] = (Ka x c) or [H3O+] = (Ka x c) for weak acid [H3O+] = (5.80 x 10-10 x 0.15) [H3O+] = 9.33 x 10-6 mol dm-3 pH = lg (9.33 x 10-6) pH = 5.03

pH values of weak bases of 0.15 mol dm-3 (Kb for the base at 25C is 7.30 x 10-10 mol dm-3)

for weak base, [OH- ] = (Kb x c) for weak base [OH- ] = (7.30 x 10-10 x 0.15) [OH-] = 1.05 x 10-5 mol dm-3 pOH = lg (1.05 x 10-5) pOH = 4.98 pH = 14.00 4.98 pH = 9.02

Bonus: One final question to ask yourself as added bonus. Does the pH of water remain the same at 7.0 for all temperatures? For those that answer yes, you are wrong. At high temperature such as 100C, the pH value is 6.14. So water is acidic at 100C? If you answer yes to that question, you are wrong again. It is just that the neutral point has shift to 6.14 for that temperature. While this might not come out in your exams, but it is always good to know to have a better understanding of the concept. Conjugate pairs

consists of an acid and a base that exchange one proton acid deprotonated forms its conjugate base base protonated forms its conjugate acid

Example: The conjugate base of HCO3- is which of the following?

A H2CO3 B CO32C CO2 D HCO2Solution: Conjugate base is formed when an acid loses one proton (eliminate option A = conjugate acid of HCO3-). Dissociation reaction of bicarbonate into hydronium and carbonate: HCO3-(aq) + H2O(l) <-> H3O+(aq) + CO32-(aq) Answer: B CO32Typical conjugate pairs

Conjugate pair favours the conjugate acid form in the presence of hydronium (H3O+). Conjugate pair favours the conjugate base form in the presence of hydroxide (OH- ). If pH (solution) > pKa (conjugate acid), the solution is basic relative to the compound, so it is deprotanated. If pH (solution) < pKa (conjugate acid), the solution is acidic relative to the compound, so it is protonated.

Example of common conjugate pairs:

carboxylic acids / carboxylates (RCOOH / RCOO- ) alkyl ammoniums / alkyl amines (RNH3+ / RNH2) phenols / phenoxides (C6H5OH / C6H5O- ) carbonic acid / bicarbonate (H2CO3 / HCO3- ) phosphoric acid / dihydrogen phosphate (H3PO4 / H2PO4- ) pH refers to the surrounding solution (environment) in which the compound exist pKa refers to the conjugate acid that exists in solution compound responds to the pH of the solution Conjugate Base RCOO- / pKb = 9 11 RNH2 / pKb = 4 5

Example of specific pairs:

Physiological compounds and their natural states

Acid RCOOH / pKa = 3 5 RNH3+ / pKa = 9 -10

Relationship of pKa and pKb an acid when deprotonated forms its conjugate base a base when protonated forms its conjugate acid Ka x Kb = 10-14

Example: What is the pKa for ammonia, given that the pKb for ammonia is 4.7? A 33 B 9.3 C 7.0 D 4.7

Solution:

the answer is not B 9.3! The compound with a pKa of 9.3 is ammonium (NH4+) the conjugate acid of ammonia ammonia is a weaker acid than ammonium, so it has a pKa greater than 9.3 pKa (HA) + pKb (A- ) = 14 is for conjugate pairs, not for the same compound.

Answer: A 33

Titration curves

quantitative reactions acid-base titration quantitative addition of a titrate acid to a base in solution (or of a titrate base to an acid in solution equivalence point when the moles of acid (H3O+) are equal to the moles of titrate base (OH-) end point of an acid-base titration the point at which the indicator changes colour

Two versions of titration Version 1: titration of a strong reagent by a strong reagent. Example: strong acid by strong base / strong base by strong acid Point of curve Species in solution Initial Before equivalence At equivalence Past equivalence Version 2: titration of a weak reagent by strong reagent. Example: weak acid by strong base / weak base by strong acid Point of curve Species in solution Initial Pure weak pH < 7 pH = pKa lg[HA] pH range pH calculation (Extra notes) OHpH > 7 pOH = -lg[OH-]excess H2O & salt pH = 7 pH = 7 Pure strong pH << 7 acid H3O+ pH < 7 pH = -lg[H3O+] pH = -lg[HX]initial pH range pH calculation (Extra notes)

acid Before equivalence At equivalence Past equivalence (there is no titration of a weak reagent with a weak reagent two weak reagent do not react with one another) Important point in curve shapes Case 1: titration of a strong acid by a strong base / titration of a strong base by a strong acid.

HA and A- pKa 1 (Buffer) A- (diluted) pH > 7 OHpH > 7

pH = pKa + lg ([A- ] / [HA]) pOH = pKb lg[A- ] pOH = -lg[OH- ]excess

the shape of the curve sigmoidal equivalence point is at pH = 7.0 (product is neutral salt and water) pH is measured on a log scale each change of 1.0 in the pH requires ten times less titrate. Example: pH = 1 to pH = 2, the hydronium concentration goes from 0.10M to 0.01M, a change of 0.09M H3O+

Example of sigmoid Case 2: titration of a weak acid by a strong base / titration of a weak base by a strong acid

titration curves exhibit an initial cusp when the reagent being titrated is weak (a lip-o-weakness) pH at half-equivalence point = pKa

titration of a weak acid by a strong base, the equivalence pH > 7.0 (because the neutralised product is a weak base / the conjugate base of the weak acid) titration of a weak base by a strong acid, the equivalence pH < 7.0 (because the neutralised product is a weak acid / the conjugate acid of the weak base)

Three types of titration curves 1. concentration effect on titration curve shape

2. strength effect on titration shape 3. polyprotic acid titration curve Indicators

an organic compound with extended conjugation weak acid (protonated) form and conjugate weak base (deprotonated) form two distinct colour when the pH of the solution is less than the pKa of the indicator (pH solution < pKa (indicator),

Indicator

pH range Colour change (acid)

Colour change (alkali) blue fuchsia (pink) orange yellow blue

Litmus Phenolphthalein Methyl orange Methyl red Bromothymol blue

4.5-8.3 8.3-10.0 3.1-4.4 4.4-6.2 6.0-7.6

red colourless red red yellow

HIn(aq) + H2O(l) <-> H3O+(aq) + In-(aq) HIn = acid (colour A) In- = conjugate base (colour B) Case 1: Environment: < pH values (concentration H3O+ is high) Le Chateliers principle: Equilibrium shifts to the left Colour: A Case 2:

Environment: > pH values (concentration H3O+ is low) Le Chateliers principle: Equilibrium shifts to the right Colour: B Case 3: Environment: [HIn] = [In-] Colour: Intermediate colour KHIn = ([H3O+] [In]) / [HIn] KHIn = indicator dissociation constant Choosing an indicator I) Strong acid Strong base Titration

pH range from 3.5 to 10.5 Suitable indicator: Phenolphthalein, methyl red, bromothymol blue)

II) Strong acid Weak base Titration

pH range from 3.1 to 7.0 Suitable indicator: Methyl orange

III) Weak acid Strong base Titration

pH range from 8.3 to 10.0 Suitable indicator: Phenolphthalein

IV) Weak acid Weak base Titration

pH range has no sharp Suitable indicator: no indicator

V) Weak Polyprotic Acids

There are few equivalence points First equivalence point = pH range at 4.6 Suitable indicator: Methyl orange, Methyl red Second equivalence point = pH range at 9.0 Suitable indicator: Phenolphthalein

Natural acid-base indicator

Anthocyanin (red in acidic solutions and blue in basic)

red cabbage leaves rose petals skin of a lemon berries hydrangea

[Bonus: it is important to understand that the pH range stated might shift very slightly depending on the indicator's concentration level in the solution and also the temperature of the solution. So take special note when you run experiments involving indicators.] Biology Buffer Diet Cola is fairly acidic. If you consumed 12 can of diet cola, you might be expected that pH in your body would become lower than normal neutral condition and you might be dying. But surprisingly, in our body blood which is a buffer that can resist changes in pH. Case 1: HCl + NaCH3COO > NaCl + CH3COOH Buffer solution containing:

Weak acid = acetic acid Conjugate base = sodium acetate

When we add hydrochloric acid (strong acid) to this solution, hydrochloric acid will beconverted into a weak acid, CH3COOH. Therefore, the overall pH of the solution relatively constant / pH value change only veryslightly. Case 2: NaOH + CH3COOH > NaCH3COO + H2O Buffer solution containing:

Weak acid = acetic acid Conjugate base = sodium acetate

When we add sodium hydroxide (strong base) to this solution, sodium hydroxide will beconverted into a weak base, NaCH3COO. Therefore, the overall pH of the solution relatively constant / pH value change only veryslightly. Henderson-Hasselbalch equation

pH = log10 Ka + log10 ([base] / [acid]) pH = pKa + log10 ([A-] / [HA]) pH = pKa + log10 ([Moles conjugate base] / [Moles conjugate acid])

This equation is used to :

determine the pH of a buffered solution. it shows that as [conjugate acid] increases, buffer pH decreases. it also indicates that if the pH is greater than the pKa, the solution is rich in conjugate base.

Example: If water is added to a buffer solution with pH = 3.96. What happen to the pH? A The pH remains the same B The pH increases slightly C The pH decreases slightly D If the pH is greater than 7, then it decreases. If the pH is less than 7, then it increases. Solution:

Addition of water to a buffer solution equally dilutes the concentration of the weak acid and its conjugate base. This means that the mole ratio of the weak base to the weak acid does not change upon the addition of water. According to the Henderson-Hasselbalch equation, the pH of the solution does not changebecause pKa is constant and the fraction has not changed. Therefore, the pH of the buffer does not change when it is diluted.

Buffers

buffer is a solution where pH remain relatively constant / pH value change only very slightly after the addition of small amount of either strong acid or strong base buffer are made of roughly equal mole mixture of a weak acid and its weak conjugate base in an aqueous solution.

Example: Explain why a solution containing a strong base and its salt does not act as a buffer solution? Solution: Addition of OH- does not shift an equilibrium toward un-ionised base, as it would with a weak base and its conjugate. Buffer Recipes

buffer can be made either by mixing the conjugate pair together or buffer can be made by partially titrating either component in a conjugate pair of weak reagents.

Case 1: Half-titrate the weak acid with strong base (Tips: a weak acid must be chosen with a pKa value close to the desired pH) Case 2:

Half-titrate the weak conjugate base with strong acid Buffers can be mixed by any of the method below:

Weak acid + the salt of the conjugate base in roughly equal mole proportions (HCOOH with HCOONa) Weak base + the salt of the conjugate acid in roughly equal mole proportions (NH3 + NH4Cl) Weak acid and roughly half of an equivalent of strong base (HOAc with half equivalent KOH) Weak base and roughly half of an equivalent of strong acid (H3CNH2 with half equivalent HCl)

Example: Which of the following combinations of solutes would result in the formation of a buffer solution? A NaC2H3O2 + HC2H3O2 B NH4Cl + NH3 C HCl + NaCl D HCl + HC2H3O2 E NaOH + HCl F NaOH + HC2H3O2 in a 1:1 mole ratio G NH3 + HCl in a 2:1 mole ratio H HC2H3O2 + NaOH in a 2:1 mole ratio Tips:

CH3COOH same with HC2H3O2. Must has roughly equal mole mixture of a weak acid and its weak conjugate base.

Solution: The solution in G contains equimolar quantities of NH4+ and NH3. The NH4+ results from the reaction. H+Cl- + NH3 > NH4+ + Cl The NH3 was present in excess. Similar situation occurs in H Answer: A, B, G and H. Example: Which of the following does not form a buffer when added to NaHCO3(s)? A NaOH(aq) B HCl(aq) C H2CO3(aq) D H2O(l) Solution:

Adding of an equivalent of NaOH to a sodium bicarbonate solution converts of the HCO3- to its conjugate base CO32-. The mixture of the two forms a buffer, so A is correct.

Adding of an equivalent of HCl to a sodium bicarbonate solution converts of the HCO3-to its conjugate acid H2CO3. The mixture of the two forms a buffer, so B is correct.

Adding an equivalent of H2CO3 to a sodium bicarbonate solution results in equal portions of the HCO3- to its conjugate acid H2CO3. The mixture of the two forms a buffer, so C is correct.

Adding water does not make a buffer, because water is amphoteric, so it does not convert sodium bicarbonate to either its conjugate acid or conjugate base. To be a buffer, there must be both a weak acid and its weak conjugate base present in solution at the same time.

Answer: D Example: If 1.0 moles of a weak acid in 1.0 dm3 of water are treated with 0.4 moles of strong base, what is the pH of the solution? (Ka for the weak acid is 2.0 x 10-4) A pH < 3.7 B pH = 3.7 C 3.7 < pH < 7 D pH > 7 Solution:

If the ratio of base to acid were 1:1, the pH would be equal the pKa. pKa is lg 2.0 x 10-4 = 4 lg 2 = 4 0.3 = 3.7 To be half-titrated, it would require 0.5 moles of strong base. At the half-titration point, the pH = pKa. With only 0.4 moles of base, the halfway point is not yet reached and there is excess weak acid relative to conjugate base (0.6 moles to 0.4 moles). Henderson-Hasselbalch equation, the pH is less than the pKa. Therefore, A is the best choice. pH is less than pKa, which is 3.7. Be aware that this question could about the [H+] as well as the pH of the solution. If a solution is half-titrated, then the Ka = [H+]. This can be tricky, but the answer is found from the Henderson-Hasselbalch equation. pH = pKa + lg (0.4/0.6), so pH < pKa.

Answer: A

Buffer Solution in Biological System

Physiological pH is to be 7.4 Venous and arterial pH vary Gastric fluids are highly acidic

Case 1: Physiological buffer = carbonic acid (in blood) Arterial blood (oxygen rich) = slightly higher pH than venous blood (carbon dioxide rich)

When water added to carbon dioxide, it would undergo the following reaction: CO2(g) + H2O(l) <-> H2CO3(aq) <-> HCO3-(aq) + H+(aq)

Equilibrium regulates blood pH that affect carbon dioxide levels (= affect the pH) and buffering of blood. The blood can compensate for the reduced uptake of oxygen by increasing heart rate and producing more red blood cells, but release of carbon dioxide is not easily adjusted.

This results, blood to be more acidic than normal (respiratory acidosis). Vice versa for the respiratory alkalosis results from the excessive loss of carbon dioxide.

Case 2: Physiological buffer = gastric fluids = rich in HCl and highly acidic.

Loss of gastric fluids results in the loss of acid from the body (metabolic alkalosis). This result, vomit or the pumping of the stomach. The acidic solution (in body) must be replenished to reduce the risk of metabolic alkalosis. Vice-versa for the food poisoning and drug overdose patients are given a solution of charcoal and water to drink to absorb the organic toxin.