Titrimetry(anEm`pnmQwQy)

Quantitative method The amount of substance(titrand) is calculated from the measured amount (usually volume)of a reagent solution(titrant or standard solution) of known concentration. The process is called Titration

For a titrimetric determination

1. 2. 3. 4. 5.

The reaction must be fast. The reaction must be stoichiometric. It must go to completion with no side reactions. Should alter a physical or chemical property at the completion of the reaction. An indicator should be available to determine this change.

Classification of titrations
From type of reaction

Acid- base titrations Precipitation titrations Redox titrations Complexometric titrations

From type of titrant used o Acidimetry

o Alkalimetry o Argentimetry o Permanganometry o Iodometry and iodimetry

Classification of titrations
From the method of end point detection Visual titrations

Electrometric (Potentiometric titrations) (Amperometric titrations) (Coulometric titrations) (Conductometric titrations)

Photometric (Colorimetric titrations.)

Gravimetric titrations

Standard solution

Primary standard (pY`}mQk pY`m`NQky)

A compound that can be weighed and diluted to get an exact concentration.

These must be of known purity, preferably 100%. reaction with the reagent to be analyzed should be stoicheometric, complete, fast and selective. easy to handle (weighing & dissolving). high molecular weight (to minimize weighing errors). readily available, inexpensive and easy to dry. stable in conditions used (in air & in solution). should not absorb water (hygroscopic) or CO2. soluble in the medium used (long term).

Examples of primary standards

Bases (For standardizing acids) Sodium carbonate (Na2CO3)-commonly used but low MW. 4-aminopyridine high purity and stability. Sodium tetraborate (Na2B4O7)
Acids (For standardizing bases) Benzoic acid Potassium hydrageniodate {KH(IO3)2} Potassium hydrogen phthalate (KHP)- most commonly 2-Furonic acid- stronger acid than KHP.

used.high MW(204.2 g/mol). High purity, thermally stable and reacts fast with NaOH and KOH.

Other common primary standards

Ag, Ag(NO3), NaCl, KCl, KBr

K2Cr2O7, KBrO3, KIO3, Na2C2O4, As2O3, Metals (Zn, Cu, Fe, Mg, Ni, Mn,) EDTA

**(NaOH,KOH, HCl, HNO3, H2SO4, H3PO4, KMnO4, Na2S2O3 are not primary standards.)

 Secondary standards (q~vQwQk pY`m`NQky)

A solution with an approximate concentration is prepared and the exact concentration is established using a primary standard.(standardized) The second material is then considered a secondary standard.

Equivalence point (smkw` l]&y)

(theoretical end point)

The point where enough titrant (stoichiometric amount) is added to completely react with the titrand(analyte).

Endpoint (an~wl]&y)

The amount of titrant required for the detection of the equivalence point.
In a titration we ideally want the equivalence point and the end point to be the same. But this seldom happens due to methods used to observe the end points. The deviation from the true value is known as the titration error.

Acid-Base titrations am|l-x;~m anEm`pn

Acid- base theories
1.
acids are substances that yield H+ in aqueous solutions. bases are substances that yield OH-.

Arrhenius theory

2.

Lewis theory
acid compounds that can accept a lone pair of
electrons. electrons.

base compounds that can donate a lone pair of

3.

Bronsted-Lowry theory
acid compounds/ions that can give up a proton
(proton donor)

base compounds/ions that can take in a proton

(proton acceptor)

HA
Acid

H + + AConjugated base

**(stronger the acid weaker the conjugated base)

BOH + H+
Base

Conjugated acid

B+ + H2O

Strong acids and bases

Acids and bases that fully dissociate in aqueous solution. eg.

HCl, HNO3, H2SO4, HClO4 .. NaOH, KOH, NaNH2 .

**in water all are of equal strength but strength depends on the medium used. eg. HCl is a weak acid in a acetic acid medium.

Weak acids and bases

Partial dissociation in the medium. H+ + Ac-

Acids HAc

Acid dissociation constant = Ka = [H+][Ac-] [HAc] Bases BOH B+ + OH-

Base dissociation constant = Kb = [B+][OH-] [BOH]

Autoprotolysis of water
H2O + H2O H3O+ + OHKw = [H3O+][OH-] [H2O]2
= ion product of water = water dissociation constant

Kw = [H+][OH-] = 1.00 x 10-14 at 250C.

The value of Kw depends on temperature.
T (0C) 0 10 25 40 60 Kw (x 10-14) 0.12 0.29 1.01 2.92 9.61

The concept of pH
pH = -log[H+]
Kw = [H+][OH-] Hence pKw = pH + pOH = 14
at 250C.

at 250C pH of pure water is 7.0 and neutral. if pH > 7.0 solution is basic if pH < 7.0 solution is acidic.

Acidity constant of a base

For a base BOH
B+ + OH-

Kb = [B+][OH-] [BOH] For the conjugated acid B+ + H2O BOH + H+ Ka = [BOH][H+] [B+][H2O]

Ka.Kb = Kw

Hydrolysis of salts (lvN jlvQc|@j~qny)

4 classes
o o o

Derived from strong acid + strong base eg. NaCl weak acid + strong base eg. NaAc strong acid + weak base eg. NH4Cl weak acid + weak base eg. NH4Ac

neutral basic acidic ??

1. Salt of strong acid and strong base

eg. NaCl + H 2O Na+ + Clstrong electrolyte

**pH of the solution is 7.00 (at 250C.)

Salt of weak acid and strong base

eg. NaAc + H2O Na+ + Ac-

A- + H2O
1-x

HA
x

+ OHx

Kh = hydrolysis constant = [HA][OH-] = Kw/Ka [A-][H2O]

But [HA] = [OH-]

Kh =[OH-]2/[A-]

since Kh is very small, [A-]= c

c = concentration of the salt in the solution

Kh = Kw= [OH-]2 Ka c

or

[OH-] = c.Kw/Ka = Kw/[H+]

Hence [H+] =Kw/ c.Kw/Ka = Kw.Ka /c pH = pKw +pKa -pc(or +log c)

eg. For an 0.05M aqueous solution of sodium benzoate at 250C.

pKw=14.0 pKa(benzoic acid)=4.2 (Ka is 6.37 x 10-5) pc =1.30 (for 0.05M) pH of the solution =7.0 +2.1 0.65 = 8.45

Salt of strong acid and weak base

NH4Cl + H2O NH4+ + Cl-

eg.

M + + H2 O
1-x

MOH
x

+ H+
x

Kh = [MOH][H+] = Kw = [H+]2 [M+][H2O] [H+] = Kw.c/Kb pH = pKw - pKb+ pc Kb [M+] = c

eg. For an 0.2M aqueous solution of ammonium chloride at 250C.

pKw=14.0 pKb(ammonia)=4.74 (Kb is 1.8 x 10-5) pc =0.70 (for 0.2M) pH of the solution =7.0 -2.37 + 0.35 = 4.98

Salt of weak acid and weak base

NH4Ac + H 2O NH4+ + Ac-

eg.

M+ + A- + H2O
a-x a-x

MOH
x

+ HA
x

Kh =

[MOH][HA] [M+][A-][H2O]

Kw Kb.Ka

x2 (a-x)2

But from acid dissociation [H+] = Ka[HA]/[A-] =Ka.x/(a-x)

[H+] =KaKh = KaKw/KaKb = Kw.Ka/kb

pH = pKw + pKa -pKb

its independent of concentrations.

eg. For an 0.2M aqueous solution of ammonium methanoate

at 250C.
pKw=14.0 pKb(ammonia)=4.74 (Kb is 1.8 x 10-5) pKa(methonoic acid) = 3.75 (Ka is 1.77 x 10-4)

pH of the solution =7.0 +1.88 2.37 = 6.51

Titration curves (anEm`pn vkY)

Plot of a variable parameter during a titration against the titrant volume

For acid base titrations the parameter is pH.

pH

base

Volume of titrant added

acid

Strong acid-strong base titrations pYbl am|l-pYbl x;~m anEm`pn

Net reaction H3O+ + OHInitial pH 2H2O
0.10M NaOH

=-log[H+] = 1.0
pH prior to equivalence point
+

0.10m HCl

At equivalence point
The cation and anion does not get involve in reactions. pH = 7.00 (at 250C)

After equivalence point (over titration)

For the titration of 50.00 mL of 1.0M HCl with 1.0M NaOH

Volume of NaOH added (mL) 0.00 (initial) 10.00 30.00 40.00 (prior to 49.00 endpoint) 49.95 50.00 (end point) 50.05 51.00 (after 60.00 endpoint) 80.00 pH of the flask 0.00 0.18 0.60 0.95 1.99 3.30 7.00 10.70 11.99 12.96 13.36

The size of the vertical region will depend on the concentration of the acid and the base

If the base is the titrant the curve is a mirror image of the one discussed.

Weak acid strong base titrations qEbl am|l-pYbl x;~m anEm`pn

eg. Titration of 50.00 mL of 1.0M acetic acid (Ka= 1.0 x 10-5) with 1.0M NaOH. Initial pH Use Oswalds dilution law

HA
c(1-x)

A- + H+
cx cx

Ka = (cx)2/c(1-x)

[H+] = Ka.ca
**for

or

pH=pKa- log ca

above eg. pH =2.5

(The pH is much higher than that of the strong acid and weaker the acid higher the pH)

Titration of very weak acids pKa<10-10) are not feasible.

pH Before the equivalence point Reaction HA + OHH2O + ApH=pKa +log[A-]/[HA]

Henderson-Hasselbalch equation

Ka = [H+][A-] [HA]

[H+] = Ka[HA] [A-]

Since Ka is small can neglect the HA dissociation Hence [HA] acid left & [A-] base reacted=salt formed

Total moles of acid left = (Ca.Va- Cb.Vb)/1000 Moles of salt formed =CbVb/1000

[H+] = Ka(CaVa- CbVb) C bV b

For our example, Titration of 50.00 mL of 1.0M acetic acid (Ka= 1.0 x 10-5) with 1.0M NaOH.

When 5.00 mL of NaOH is added [H+] = Ka(CaVa- CbVb) Cb V b [H+] = 1 x10-5.(1.0x50.00-1.0x5.00) 1.0x5.00 = 4.04

Half equivalence point when [HA]=[A-]

Then, pH = pKa

pH=pKa +log[A-]/[HA]
Henderson-Hasselbalch equation

At equivalence point All acid has reacted. And solution is like when a salt is dissolved pH = pKw +pKa -pc(or +log c)
C is the concentration of salt at the equivalence point.which is equal to ca.Va/(Va+Vb)

For our eg. pH= 7.0 +2.5 -0.15 =9.35

After the equivalence point, the excess strong

base governs the pH of the medium and calculations are same as in strong acid- strong base case.

For the titration of 50.00 mL of 1.0M HAc with 1.0M NaOH Volume of NaOH added (mL) 0.00 (initial) 10.00 30.00 40.00 (prior to 49.00 endpoint) 49.95 50.00 (end point) 50.05 51.00 (after 60.00 endpoint) 80.00 pH of the flask 2.50 4.40 4.82 5.60 6.69 8.00 9.35 11.00 12.29 13.22 13.57

Usually the weak acid is the titrand. But if the acid is in the burette, Till equivalence point is like strong acid-strong base case. pH at equivalence point ??? After equivalence point [HA] =ca.Va*/(Va+Vb)

Weak acid

[salt]=[A-]= cb.Vb/(Va+Vb)
Strong base

[H+]=Ka.[HA]/[A-]=Ka.(ca.Va*/ cb.Vb)

**Since the titrant is weak need time to dissociate and react.

Polyfunctional acids with strong base

For a diprotic acid

H2A H+ + HA-

HA-

H+ + A2-

For the 2 steps to be titrated separately (to get 2 well defined equivalence points) Ka1 Ka2 >103
(for 1 - .001M acids)

Strong acid weak base titrations pYbl am|l- qEbl x;~m anEm`pn

Treat like previous case using Kb instead of Ka

eg. Titration of 50.00 mL of 1M NH4OH with 1M HCl

NH4OH c(1-x) NH4+ + OHcx cx Kb = [NH4+][OH-] [NH4OH]

Initial pH
[OH-]=Kb.cb

Before equivalence point pKb =pOH log [NH4+]/[NH4OH] ([salt]/[base])

But pH +pOH =pKw Hence, pH = pKw- pKb - log[salt]/[base]

[salt]/[base]=amount of acid added/amount of base left = ca.Va/(cb.Vb-ca.Va)

At equivalence point Treat as hydrolysis of salt of weak base strong acid

pH = pKw - pKb+ pc
c= concentration of salt at equivalence point = cb.Vb/(Va +Vb) **Equivalence point is in acidic pHs & depend on the strength of the base.

Weak acid weak base titrations qRbl am|l-qRbl x;~m anRm`pn

Feasibility depends on both dissociation constants Ka&Kb.

Titration of anion of weak acid (conjugated base) with strong acid

eg. Acetate ion Ac- +H2O HAc + OHH+

NaAc(aq) + HCl(aq)

HAc + Na+ + Cl-

eg. Borate ion

B4O73- + 2H+ +5H2O 4 H3BO3 Ka of boric acid 6.4 x10-10

Titration of carbonate & bicarbonate with a strong acid

CO32- + H+
HCO3- + H+

HCO3H2CO3 H2O + CO2

For carbonic acid

Ka1=4.5 x10-7 molL-1 & Ka2=5.6 x10-11 molL-1

Hence for carbonate ion

Kb1=1.8 x10-4 molL-1 & Kb2=2.2 x10-8 molL-1 Kb1/Kb2 104 and 2 separate equivalence points

Acid-base indicators am|l-x;~m qr\Xk

Equivalence point detection in acid base titrations is commonly done by visual detectors. Spectrometric, potentiometric, thermometric detection is also used. They are weak organic acids or bases. Their color differs from the color of their conjugate base or acid.

One color indicators eg. Phenolphthalein (colorless-magenta)

Two color indicators eg. Methyl orange (red-yellow)
They change color in a definite pH range called transition range. This range depends on the acidity constant(or basisity constant) of the indicator. In pH above the range indicator is predominantly in its base form & in lower pHs in its acidic form.

o o o

HIn
(acid form)

H+ + In(base form)

Indicator constant = Kin =[H+][In-]/[HIn]

pKIn= pH - log [In-]/[HIn]

pH = pKIn + log [In-]/[HIn] **When both forms are present the eye detects the predominant color(usually taken as when 10 times more than the other color)

pH = pKIn 1

In order to be a good acid base indicator

It should be weaker than the species reacting

Must be present in low concentrations (not significantly interfere with the equivalence point) Must be high molecular weight molecules. The 2 colors should be markedly different (ideally complementary) The color/s should be intense to give a sharp end point.(the transition range should be small)

Choosing of a suitable indicator

The color change range (pKIn) & the vertical portion of the titration. Ka,Kb, of the acids & bases Concentration of acids & bases Temperature Effect on kw,Ka, Kb.. Effect on Kin Stability of colors Solvent medium Strength of acids & bases Solubility of indicator

Litmus

Litmus is a water soluble dye extracted from certain lichens and absorbed on to filter paper. The active ingredient of Litmus is called Erythrolitmin. Color change range 4.5- 8.3 (pKIn 6.5) Acid color red, base color blue (purple inbetween)

Phenolphthalein

pKIn = 8.7 (range 8.3- 10.0) Colorless Pink (magenta) acidic basic

*End point in basic medium If base in flask, the end point is when medium is colorless. If acid in flask, the end point is when medium is slightly pink

Methyl orange

pkIn = 3.5 (range 3.2-4.4)

Red acidic orange yellow basic

*End point in acidic medium If base in flask, the end point is when medium is orange. If acid in flask, the end point is when medium is yellow

Methyl red

pkIn = 5.0 (range 4.2-6.2)

Red acidic orange yellow basic

Bromothymol blue

pkIn = 7.3 (range 6.2-7.6)

yellow acidic Green blue basic

Strong acid(1M)-strong base (1M) titration

Strong acid(1M)-weak base(1M) titration

Weak acid(1M)-strong base (1M) titration

Weak acid(1M)-weak base (1M) titration

CO32-(1M)- strong acid titration(1M)

Screened indicators

To get a pronounce color at the end point add a dye with the indicator. eg. Screened methyl orange

Red acidic

orange

yellow basic

Add a blue dye purple

grey

green

Buffers (s~v`r]k qY`vN)

L 11

A mixture of a conjugate acid base pair It tends to resist changes in pH when an acid or base is added. Commonly used when pH must be maintained at a relatively constant value and in many biological systems.

Effect of adding a acid to a buffer

eg. if add 10 mL of 1.0 M HCl to 100 mL of pure water at pH 7.

if add 10 mL of 1.0 M HCl to 100 mL of a solution containing1.0M HA and 1.0M A- at pH 7. (pKa=7)

The added 10 mL of acid will react with the conjugate base,converting it to the acid. So we would have 0.09 moles of base form and 0.11 moles of the acid form.

When 100mL of 1.0M HCl is added virtually all Ais converted to HA and the calculation of pH has to be done using KA.

At this point we have exceeded the buffer region of our system. The upper limit can be calculated too.?????

Buffer capacity(s~v`r]k {`rQw`v)

The number of moles of a strong acid or base that causes 1 liter of a buffer solution to undergo a pH change of 1.00.

Compelximetric titrations (sAkWr\NmQwQk anEm`pn)

Based on reactions forming a stable complex when titrant and titrand react. The reaction has to be fast and stoicheometric

The complex has to be soluble in the medium

(insoluble complex forming reactions are considered under precipitation titrations)

Usually involves a cation of a metal (metal complexes)

M
Metal

+ nL
ligand
(complexing agent)

MLn
complex

Kst (or KML) = [MLn] = [M][L]n

formation constant of complex (stability constant)

Classification of ligands

Monodentate eg. Cl, Br, CN, CO, NO2, H2O, NH3 (binds to the metal, donating one pair of electrons)
Bidentate
forms two bonds with the central atom

eg. NH2CH2CH2NH2 (en)-ethylene diamine Chelating ligands

8-hydroxyquinoline

Dimethyl glyoxime (DMG)

1,10 phenanthroline (phen)

Diphenyl carbazide (carbazone)

Polydentate ligands

EDTA(ethylenediamine tetraaetic acid)

Most common complexing agent.

Insoluble in water. Need to add NaOH to dissolve. Usually use the disodium salt (Na2H2Y) Both are primary standards

Forms 1:1 complexes with most of the metals (except group 1A)
Complexes are water soluble.

The molecule contains six donor groups

Forms a hexadentate complex with metals

pKa1=1x10-2
pKa3= 6.9 x10-7

pKa2=2.1x10-3
pKa4=7.4 x10-11

2 strong acid groups, major ion is H2Y2-

Mn+ + H2Y2-

MY(n-4) + 2H+

Higher the acidity lower the formation constant (stability of complex formed)

Only strong complexes can be used at low pH.

buffering is very essential in EDTA titrations pH stability of M-EDTA complexes
Minimum pH of complex metal ion

1-3 4-6 8-10

Zr4+, Hf4+, Th4+, Bi3+, Fe3+, Al3+,Pb2+,Cu2+,Zn2+,Co2+,Ni2+,Mn2+,Fe2+,Cd2+,Sn2+ Ca2+, Sr2+, Ba2+, Mg2+,

Titration curve
is plotted against volume of EDTA added. EDTA is usually the titrant

EDTA

similar to acid base titration curves. pM (for pH)

metal

pM = -log[M]

eg. 100 mL of 0.1M metal(KMY=1.0x1011) titrated with 0.1M EDTA

Initial pM pM = -log[M] =1.0

pM before the equivalence point

[M] = unreacted metal ions = CmVm- CLVL

total volume Vm+VL

pM at equivalence point
All metal ions are complexed. [complex] =[MY]= CmVm

Vm+VL(at endpoint)
But, KMY=[MY]/[M][Y] and [M]=[Y]

[M] =[MY]/KMY
Stronger the complex, lower the [M], higher is pM which leads to a larger vertical portion.

After the equivalence point

Amount of free ligand from dissociations of complex is negligible.

[Y] = extra ligand added = CLV*L total volume Vm+VL [MY] = initial metal in solution total volume KMY=[MY]/[M][Y] = CmVm Vm+VL

[M] = CmVm KMY.(CLV*L)

The vertical portion of the curve is dependent on Stability constant of the complex pH of medium Temperature Metal and ligand concentrations

Indicators

L 12

Visible and instrumental methods are used to detect the endpoint. Visible indicators are called metalochromic indicators or metal indicators. These form weaker complexes with metals, than EDTA. The complexed and uncomplexed(free) forms are different in color.

M + In
free

MIn
m-complex

Since it is easier to react with free metal EDTA will not react with MIn till free metal is almost over.

EBT (Eriochrome Black T)

A triprotic acid and can act as acid base indicator too. The metal-In complexes are wine red in color. The color of the free indicator is pH dependent.

H2InRed
pH 6-7 pKa1 6.3

HIn2pKa1 11.6

In3-

Blue pH 11-12 Orange

Only useful in the range of pH 7-11

Other metal indicators

Calmagite
Same as EBT, useful range = 8.1-12.4

NAS
Red violet at very acidic pH & red orange at pH 3.5 Metal complex pale yellow with Cu, Zn & Pb

DMG

for detection of Ni

8 hydroxyquinoline

For Mg, Zn, Cu, Cd, Pb, In, Al, Bi, Ga, Th, Zr,

Potton & Reeders (HHSNNA)

(2 hydroxy-1-(2 hydroxy-4-sulpho-1-napthylazo)-3-naphthoic acid)

for Ca Color change wine red to blue pH range extends beyond 13.

Other compleximetric ligands

NITA or NTA (nitrilotriacetic acid) CDTA or DCTA (trans-1-2 diaminocyclohexane N,N,N,N

tetraacetic acid)

EGTA (2,2 ethylenedioxybisethyliminodiacetic acid) TTHA (triethylene tetraamine N,N,N,N,N,N hexaacetic acid)

Types of EDTA titrations

1. Direct titrations
Direct addition of EDTA to a metal containing solution. eg. Ca2+, Zn2+
EDTA
Standard metal

2. Back titrations
Excess EDTA is added to the analyte solution and the unreacted EDTA is titrated with a standard metal solution. eg. Ni2+ Used for analysis of slow reactions, buffer effected complexes, & when no indicator is available
Metal analyte

+ excess
EDTA

3.

Replacement titrations

eg. Hg2+, Ag+ For metals that does not give a clear color to the indicator. M +MgY MY + Mg

4. indirect titrations
Determination of anions that form precipitates with metal ions

eg. CO32-, CrO42-, S2-, SO42The precipitate formed is filtered, washed and excess EDTA is added. The unreacted EDTA is titrated with Mg2+.

Masking

Exclusion of the action of an interfering substance, by adding appropriate reagent By precipitation, oxidation, reduction complexation or a mix of these actions.

EDTA titrations
Addition of anion of higher binding strength to the metal ion than EDTA. Masked ions does not participate in the titration. eg. Mg2+ is titrated at pH 10, but Ba2+ can also complex. Masking agent- sodium sulfate BaSO4 will ppt. And do not even have to filter off. precipitation masking

CN- as masking agent

Will form stable complexes with Fe, Cu, Hg, Co, Ni, Cd, Zn and noble metals but complexes with Zn and Cd are weak.hence can demask by adding formaldehyde.

Think!- how can you get the concentration of Ca2+, Zn2+ and Ni2+ in a mixture by using EDTA titrations?
The Fe cyano-complex is colored and will interfere the end point detection. Hence H3PO4 is added to mask Fe.

OH- (high pH, above 11) will mask Mg2+

used in determination of Ca2+ in the presence of Mg2+

NH3 can mask Ag against Cl- but not IOxidation will mask Cr from precipitation as hydroxide. (Cr3+ to Cr7+)

Precipitation titartions (avk~@;~pNmQwQk anEm`pn)

The analyte forms a sparingly soluble complex with the titrant. Not all precipitation reactions can be used. They have to be
Fast reactions
Having reproducible product composition Low solubility of precipitate Having a method locate the endpoint

Precipitations are generally slow, co-precipitation and colored dispersed precipitates making endpoint detection hard limits precipitation titrations to Argentimetry (X & CN) and BaSO4.

Titration curve

AgNO3

For Cl- titration with AgNO3 The plot of pCl with the concentration of AgNO3 added

Cl-

eg. 100 mL of 0.1M NaCl titrated with 0.1M AgNO3 (Ksp(AgCl)=1.0x10-10)

Initial pCl pCl = -log[Cl-] =1.0

pCl before the equivalence point

[Cl-] = unreacted Cl- ions = CClVCl- CAgVAg total volume pCl at equivalence point All Cl- ions are reacted.but due to sparingly solubility Ksp=[Ag+][Cl-] [Cl-] =[Ag+]= Ksp
Lower the solubility product larger the vertical portion of the curve

VCl+VAg

After the equivalence point

Amount of free Ag+ from dissociation of precipitate is negligible. [Ag+] = extra AgNO3 added = CAgV*Ag total volume VCl+VAg Ksp= [Ag+][Cl-]

[Cl-] = Ksp.(VCl+VAg) CAgV*Ag

The size of the vertical portion depends on the Ksp, concentration of reaction species, solvent medium and the temperature. Side reactions(presence of impurities) and pH effects the vertical portion on some cases.

Endpoint detection

Potentiometric detection

use ion selective electrode (like pH meter) Ag/AgCl electrode is sensitive to changes in [Ag+] and[Cl-] concentrations

Mohr method
Use CrO42- ion to detect the end point. The Ksp difference between AgCl and Ag2CrO4 will not ppt Ag2CrO4 till the endpoint. (see fractional precipitation) Ag+ + Cl- AgCl (titration reaction) 2Ag+ + CrO42- Ag2CrO4(at end point)
brick-red

Volhard method Excess Ag+ is added and AgCl is filtered off. Excess Ag+ is titrated with SCN-. Fe3+ acts as indicator and give red Fe(SCN)2+ at the end point.

 Fajans method
Use a adsorption indicator like dichlorofluorscene(for Cl-)
Detect the change in primary adsorbed layer.
Until the equivalence point Cl- is the primary adsorbed ion and the outer surface is negative. Which repel the indicator.

After equivalence point Ag+ is the primary ion and attracts the indicator.

Absorbance & colorimetry