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ANALYTICAL CHEMISTRY
Analytical Chemistry
• Branch of Chemistry that deals with the analysis, identification, separation and
composition of matter
• Involves methods used to identify the substances that are present in a sample
(qualitative analysis) and the exact amount of the identified substances
(quantitative analysis)
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Vergel C. Bungay Analytical Chemistry
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• Crystalline – particles with size ranging from 100 microns or greater; these
particles settle readily and easily filtered
• Particle size is usually affected by temperature, concentration of reactants,
solubility of precipitate and mixing rate
b. Appearance. Precipitates may appear to be colloidal (S) , curdy (AgCl), fine
crystal (BaSO4), coarse crystal (PbCl2) or gelatinous (Al(OH)3)
c. Relative supersaturation (von Weimarn ratio)
Q −S
relative supersatur ation =
S
where Q = concentration of the solute as precipitation begins and S = solubility
of the precipitate
• In order to obtain low relative supersaturation and form a crystalline
precipitate, Q must be minimized and S must be maximized. The following
methods are done to accomplish such conditions:
increase the temperature during precipitation (to maximize S)
precipitate from dilute solution (to minimize Q)
slow addition of precipitating agent with stirring (to minimize Q)
2. Mechanism of precipitation
Precipitation is assumed to occur in two ways:
a. Nucleation
• Prevails at high relative supersaturation
• Results in the formation of large number of small particles
b. Particle growth
• Prevails at low relative supersaturation
• Results in the formation of small number of large particles
3. Colloidal precipitates
a. Electrical nature of colloidal suspensions
• Suspensions, which are stable since these particles are either positively or
negatively charged, hence repel each other
• By heating, stirring and addition of electrolyte causes this suspension to
combine together and form a readily filterable solid
• This process of converting a colloidal suspension into a readily filterable
solid is called coagulation or agglomeration
b. Adsorption of colloids
• Ions are attached directly to the
solid surface and comprise the Primary
primary adsorption layer Adsorption
Layer
• The charge of this layer is
dependent on the charge of the
ion present in excess
• A charged primary adsorption
layer attracts excess oppositely Counter
Ion
charged ions to form a secondary Layer
layer or counter-ion layer
• These ions, held by electrostatic
forces have higher mobility compared to the ions in the primary layer
• The two layers, which constitute an electrical double layer, prevent other
particles to come close thus inhibits the formation of larger aggregates
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E. Acid-Base Titration
1. Theories of acids and bases
Theories Acid Base
substances that substances that
Arrhenius theory dissociate in aqueous dissociate in aqueous
Svante August Arrhenius (1859-1927)
solution to form aH3O+ solution to form bHO–
Brønsted-Lowry theory
Johannes Nicolaus Brønsted (1879-1947) proton donor proton acceptor
Thomas Martin Lowry (1874-1936)
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Vergel C. Bungay Analytical Chemistry
4. Calculation of pH
• At 25°C, the ion product constant for water, KW is equal to 1.00 × 10–14
• At this temperature… pK W = pH + pOH = 14
• For a dilute solution at 25°C in which the contribution of water to the amount
of H3O+ and HO– in solution and the correction due to activity coefficients are
negligible, the following formulas can be used to calculate the pH:
a. Strong acids (SA) and strong bases (SB)
• HA + H2O H3O+(aq) + A–(aq) (SA): pH = −log[M SA ]
• MOH M+(aq) + HO–(aq) (SB): pH = 14 + log[M SB ]
b. Weak acids (WA) and weak bases (WB)
• HA + H2O H3O+(aq) + A–(aq) (WA): pH = − 12 log[K a M WA ]
• B + H2O BH+(aq) + HO–(aq) (WB): pH = 14 + 12 log[K b M WB ]
c. Hydrolysis of salts
• As a general rule, salts coming weak acids or weak bases hydrolyze in water,
that is, only the strong conjugate hydrolyzes in water
• Acidic salt (AS) is formed from the reaction of a strong acid and weak base
HCl(aq) + NH3(aq) NH4+(aq) + Cl–1(aq)
SA WB SCA SCB
Since only the strong conjugate hydrolyzes in water…
NH4+(aq) + H 2O NH3(g) + H3O+(aq)
K [NH 3 ][H 3O + ] M
Kh = W = +
(AS): pH = 7 − 12 log AS
Kb [NH 4 ] Kb
• Basic salt (BS) is formed from the reaction of a strong base and weak acid
NaOH(aq) + HCN(aq) Na+(aq) + CN–1(aq) + H 2O
SB WA WCB SCA
Since only the strong conjugate hydrolyzes in water…
CN–1(aq) + H 2O HCN(g) + HO– 1(aq)
K [HCN][HO−1 ] M
Kh = W = −1
(BS): pH = 7 + 12 log BS
Ka [CN ] Ka
• Neutral salt (NS) is formed from the reaction of a strong base and strong acid
• Salts from weak acid and weak base (WAB) will have the following
hydrolytic equilibrium expressed by the equation
NH4+(aq) + CN–1(aq) + H 2O NH4OH + HCN
KW [HCN][NH 4 OH ] K K
Kh = = −1 +
(WAB): pH = − 12 log W a
K a K b [CN ][NH 4 ][H 2 O] Kb
• –1 –2
Amphoteric salts (HA or HA )ionize as a weak acid and also a Brønsted
base that hydrolyzes
H 3A + H 2O H 3O + + H2A–1 Ka1
–1
H 2A + H 2O H 3O +
+ HA–2 Ka2
HA–2 + H 2O H 3O + + A–3 Ka3
K K + K a1K a2 [H 2 A −1 ]
pH of H 2 A −1 = − 12 log W a1 ≈ − 2 log[K a1K a2 ]
1
K a1 + [H 2 A −1 ]
K K + K a2 K a3 [HA −2 ]
pH of HA − 2 = − 12 log W a2 ≈ − 2 log[K a2 K a3 ]
1
K a2 + [HA − 2 ]
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To account for the contribution of water to either H3O+ or HO–1 in solution, use the
following scheme:
weak acid (WA)
pH = −log(x )
strong base (SB) acidic salt (AS)
KA WA
K
WB
K= B
x + Mx − K W = 0
2
x + Kx − MK = 0
2
K W /K B AS
K W /K A BS
pH = 14 + log(x ) weak base (WB)
strong acid (SA)
basic salt (BS)
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• Another method requires two duplicate samples. One sample is treated with
phenolphthalein and the other with methyl red. Volumes of titrant required to
reach the phenolphthalein and methyl red endpoints are recorded as V 0-Ph and
V0-MR, respectively.
• m-Cresol purple can also be used to detect phenolphthalein alkalinity (P)
while bromocresol green or methyl orange for the total alkalinity (T)
Table 10. Alkalinity relationships
Result from titration NaOH Na2CO3 NaHCO3
V0-Ph > VPh-MR V0-Ph – VPh-MR 2VPh-MR 0
V0-Ph < VPh-MR 0 2V0-Ph VPh-MR – V0-Ph
V0-Ph = VPh-MR 0 2V0-Ph = 2VPh-MR 0
V0-Ph ≈ 0 ; VPh-MR > 0 0 0 VPh-MR
V0-Ph > 0 ; VPh-MR ≈ 0 V0-Ph 0 0
Note: If analysis involves measurement of volume due to total alkalinity (V0-MR), use the
conversion: VPh-MR = V0-MR – V0-Ph
The following relationship can be summarized using the following diagram:
• Defined as the mass (mg) of KOH required to saponify one gram of fat or oil
• Can be used to determine the approximate molar mass of fat or oil
• The sample is refluxed with ethanolic KOH and the resulting solution is
titrated with standard HCl
mL
(Vblank − Vwith
mL
samplel )(M HCl )(56.10)
Sap Value =
gram of fat or oil
168,300
Molar Mass of Fat or Oil =
Sap Value
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Vergel C. Bungay Analytical Chemistry
F. Precipitation Titration
1. Important terminologies
• Saturated solution – solution that contains the maximum amount of solute
dissolved in a given amount solvent at a specific temperature
• Solubility – the maximum amount of solute dissolved in a given solvent at a
specific temperature
• Solutions that contain dissolved solute less than the maximum are called
unsaturated while those that contain dissolved solute more than the maximum
are called supersaturated solutions
2. Solubility rules for ionic compounds in water at 25°C
Soluble compounds Insoluble compounds
All nitrates, bicarbonates, chlorates All carbonates, phosphates, chromates
and compounds containing alkali and sulfides except that of alkali metal
metal ions and ammonium ion. ions and ammonium ion
All halides except that of Ag+, Hg22+
and Pb2+ All hydroxides except that of alkali
All sulfates except that of Ag+, Ca++, metal ions and Ba++
Sr++, Ba++ and Pb++
3. Solubility product constant (KSP)
• Consider an aqueous saturated solution of a sparingly soluble salt represented by
the equation:
AxBy (s) x A+y (aq) + y B–x(aq)
The equilibrium constant for this reaction would be:
[A + y (aq) ] x [B − x (aq) ] y
K eq =
[A x B y(s) ]
However the concentration of the solid AxBy in the solution will be constant (the
ratio of the number moles of AxBy and the volume of the solid is constant). Thus,
K SP = K eq [ A x B y(s) ] = [A + y (aq) ] x [B − x (aq) ] y
Table 11. Solubility product constants at 25°C
COMPOUND KSP COMPOUND KSP
AgCl 1.82 × 10–10 Mg(OH)2 7.10 × 10–12
AgBr 5.00 × 10–13 Ca(OH)2 6.50 × 10–6
AgI 8.30 × 10–7 PbCl2 1.70 × 10–5
BaCO3 5.00 × 10–9 PbI2 7.90 × 10–9
Ba(IO3)2 1.57 × 10–9 Hg2Cl2 1.20 × 10–18
Al(OH)3 3.00 × 10–34 Hg2Br2 5.60 × 10–23
CaCO3 (calcite) 4.50 × 10–9 Hg2I2 4.70 × 10–29
4. Argentometric titrations
• One of the oldest analytical techniques that started in the mid–1800’s
• Silver nitrate (AgNO3) is commonly used as titrant and the end point are
observed as follows:
a. Formation of a secondary colored precipitate – Mohr method
• Developed by Karl Friedrich Mohr (1806-1879) in 1865
Titrant: AgNO3
Titration reaction: Ag+(aq) + Cl–1(aq) AgCl(s)
white
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Indicator: K2CrO4
Indicator reaction: 2Ag+(aq) + CrO4–2(aq) Ag2CrO4(s)
yellow red
• In practice, the indicator concentration is kept between 0.002 M to 0.005 M
• Titration is done at a pH of 8 to avoid precipitation of silver as hydroxide
(above pH of 10) and eliminate formation of HCrO4–1 (below pH of 6) which
results to consumption of more titrant
• Usually a low concentration of chromate is desired to detect the end point
clearly since a chromate ion imparts an intense yellow color
b. Formation of a colored complex – Volhard method
• Developed by Jacob Volhard (1834-1910) in 1874
Titrant: KSCN
Back titration: Ag+(aq) + Cl–1(aq) AgCl(s)
excess white
Ag+(aq) + SCN–1(aq) AgSCN(s)
white
Indicator: ferric alum, NH4Fe(SO4)2⋅12H2O
Indicator reaction: Fe+3(aq) + SCN–1(aq) Fe(SCN)+2(aq)
red
• Titration is done in acidic medium using HNO3 with indicator concentration
of about 0.01 M
• For the titration of chloride, the resulting precipitate is filtered off before the
back titration since it reacts with the titrant and is more soluble than AgSCN
• For the titration of iodide, the indicator is not added until all iodide is
precipitated since the dissolved iodide is oxidized by the ferric ion
c. Formation of a colored adsorption complex – Fajans Method
• Developed by Kazimierz Fajans (1887-1975) in 1926
Titrant: AgNO3
Titration reaction: Ag+(aq) + Cl–1(aq) AgCl(s):Cl–1. . . . DCF–1
excess white greenish-yellow
Indicator: fluorescein, dichlorofluorescein or eosin
Indicator reaction: Ag+(aq) + Cl–1(aq) AgCl(s):Ag+1:DCF–1
excess white pink
• Before the equivalence point, chloride anion adsorbs to the precipitate in the
primary adsorption layer and drives the adsorption dye anion away by
electrostatic repulsion and the dye imparts a greenish-yellow color in
solution
• As soon as the equivalence point is just exceeded with the presence of excess
silver ion, this ion now adsorbs to the precipitate in the primary adsorption
layer where the oppositely-charged adsorption dye anion adsorbs to the
counter-ion layer and imparts a pink color in solution
• For titration of chlorides, fluorescein may be used at an optimum pH range
between 7-10 while dichlorofluorescein is used in acidic solution of pH
greater than 4.4
• For bromides, iodides and thiocyanates, eosin is used for titration in acidic
medium of pH between 1-2 imparting magenta color at the end point
• Dextrin is added to prevent excessive coagulation of the AgCl precipitate
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G. Complexation Titration
1. Important terminologies
• Ligand – molecule or ion which possesses at least one unshared pair of electron
capable of forming coordinate covalent bond with an ion
• Coordination complex or metal complex – formed when a metal ion is bonded to
monodentate ligands
• Chelate complex – formed when a metal ion is bonded to a polydentate ligand
• Chelants – chemicals that form soluble complex molecules with a metal ion
which results to inactivation of the ion’s ability to react with other elements to
produce precipitates
2. Titration methods involving complexes
a. Determination of cyanide – Liebig method
• The titration is carried by the dropwise addition of AgNO3 in a solution of a
cyanide forming a soluble cyanide complex of silver:
2CN–1 + Ag+ Ag(CN)2–1
• The endpoint of the titration is the formation of a permanent faint turbidity:
Ag(CN)2–1 + Ag+ Ag [Ag(CN)2](s)
b. Determination of nickel
• An ammoniacal solution of nickel is treated with a measured excess of
standard cyanide solution:
Ni(NH3)6+3 + 4CN–1 + 6H2O Ni(CN)4–1 + 6NH4OH
• The excess cyanide is determined according to the Liebig method
c. Titration with ethylenediaminetetraacetic acid (EDTA)
• The structure suggests six potential sites (hexadentate) for metal bonding –
the four carboxyl groups and two amino groups
• Reagents for EDTA titration
Free acid, H4Y – can be used as a primary standard when dried for
several hours from 130°C to 145°C and dissolved completely with small
amount of base
Disodium EDTA dihydrate, Na2H2Y⋅2H2O – analytical reagent grade is
commercially available and usually dried at 80°C for 24 hours
NH3-NH4Cl buffer solution (pH = 10) – prepared from 17.5 grams of
NH4Cl and 142 mL of concentrated NH3 and
• Indicators for EDTA titration
Eriochrome Black T or Solochrome – used for titrations with pH more
than 6.5 since it polymerizes in strongly acidic solutions; color changes
between pH range of 7-11 from royal blue to wine red;
Calmagite – similar to EBT but color change is sharper and its aqueous
solution is stable; used for titration at pH = 10 using NH3-NH4Cl buffer
• Solutions of EDTA combines with any metal ions in a 1:1 ratio
O
C
O OH O O
H2C H2
C CH2 O C C C
N O
HO N CH2 CH2 H2C
+ M+n M
H2C H2C N OH H2C
N O
C C
C OH H2C C H2
H2C
O
O
O O C
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• Step 2: Identify oxidation and reduction reactions and indicate the number of
electrons lost or gained, respectively
Oxidation: NO2–1 NO3–1 + 2e–
+3 +5
Reduction: MnO4–1 + 3e– MnO2
+7 +4
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• The equilibrium constant and the standard electrode potential are related as
follows:
nε°
log K = (T = 298.15 K, ε = 0 and Q = K)
0.05916 V
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(VmL,sample
Na 2S2 O 3 − VNa
mL, blank
S O M Na )( 2S 2 O 3
) 1 I2
2 Na 2S2 O 3
×
253.80 mg I 2
1 mmol I 2
× 101 cg
mg
Iodine Number = 2 2 3
(VmL,sample
Na 2S2 O 3 − VNa
mL, blank
S O M Na )( 2S 2 O 3
) 1 meq Na 2S2 O 3
1 mmol Na 2S2 O 3
Peroxide Value = 2 2 3
(V mL
Na 2S2 O 3 )(M Na 2S2 O 3 )× 1 mmol O 2
4 mmol Na 2S2 O 3
× 1 mmol O2
32 mg O
Dissolved oxygen = 2
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(VmL,blank
Fe + 2
− VFe
mL,sample
+2 )( )
M Fe +2 ×
1 mmol K 2 Cr2 O 7
6 mmol Fe + 2
× 4 mmol K
6 mmol O 2
2 Cr2 O 7
× 1 mmol O2
32 mg O
COD = 2
εbVS CS εbVX C X
As = + = kVS CS + kVX C X = mCS + b
VT VT
where k = εb/VT, m = kVS and b = kCXVX
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2. Analysis of mixtures
• The total absorbance of a solution at a given wavelength is equal to the sum of the
absorbances of the components in the mixture
At λ1: A1 = ε x1 bC x + ε y1 bC y
At λ2: A 2 = ε x 2 bC x + ε y 2 bC y
3. Photometric titration
• Plot of absorbance versus volume of titrant where the curves consist of two
straight line regions with different slopes
• The end point is the intersection of the extrapolated linear regions
2. Analytical methods classified as micro analysis uses sample mass ranging from
a. < 1 mg b. 1-10 mg c. 10-100 mg d. > 100 mg
3. Chemical which are tested by the manufacturers showing the actual percentages of
impurities and labeled on the containers are called __________.
a. reagent grade chemicals c. certified reagent
b. analytical reagent d. all of these
4. Platinum crucibles can be used for the following processes without significant loss
except
a. Fusion with sodium carbonate, borax or alkali bifluorides
b. Evaporation with hydrofluoric acid
c. Ignition of oxides of Ca and Sr
d. Heating with sulfides
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