Chem 28.1 Experiment No.

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 Accuracy vs. precision
Statistical concepts
Measures of central tendency
Measures of precision
Measures of accuracy
Confidence interval
Detection of outliers (Grubbs test)
Error propagation

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 Mean
Measure of central value that estimates true
value
Assumes that data are randomly scattered
Not very robust
Standard deviation
Measures how data are scattered around the
mean
More useful when expressed in relative terms
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 Pooled standard deviation
For assessment of precision of a method
Confidence limits and interval
An interval where is expected to lie with a
certain degree of probability (confidence level)
Size of CI depends on how well s estimates
Grubbs test
To objectively reject or retain an outlier
Assumes a normal distribution
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 No systematic or gross errors
Data set must be ideally large

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 Systematic or determinate errors
Method errors
Instrument errors
Personal errors
Random or indeterminate errors
Gross errors (blunders)

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 How do the statistical parameters between
two data sets compare
No definite trend
But more reliable when data set is larger
Use of forceps
To avoid introduction of moisture and other
particulates

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Chem 28.1 Experiment No. 2
 Involves measurement of mass
Types of gravimetry
Volatilization gravimetry
Direct
Indirect
Precipitation gravimetry

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 Essential water
Water of crystallization
Water of constitution
Non-essential water
Adsorbed water
Sorbed water
Occluded water

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 Direct method: moisture is trapped in
desiccant and weighed
Indirect method: loss of mass upon drying
Karl Fischer titration
Based on a redox reaction between I2, SO2 and
water in alcohol
Selective to water
Instrumental methods (e.g. spectroscopy,
coulometry, etc.)
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 Moisture content varies with atmospheric
conditions; thus, it varies with space & time
More accurate to report nutrient content in
dry basis
Rate of nutrient release is affected by amount
of moisture
Other practical reasons

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 Constant weight = mass of object when no more
moisture can be removed from it
Heating/drying: to remove adsorbed moisture
(note that essential water is retained)
Cooling requires desiccant in a desiccator
Desiccator: used to equilibrate sample to a very low
moisture level
Desiccant: substance that absorbs moisture
CaSO4: blue when fresh; pink means it should be
dried/replaced

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 Constant weight is achieved when successive
readings are within 0.0003 g (0.3 mg)
Tolerance of analytical balance: 0.0002 g
Uncertainty between two successive readings:
0.0002 2 + 0.0002 2 = 0.0003
Weighing by difference
Minimizes moisture build-up
Eliminates systematic error (how?)

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 Cooling before weighing
Apparent weight < true weight when heated
Rationale for grinding sample
To provide greater surface area
Possible sources of error?

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Chem 28.1 Experiment No. 3
 Precipitation gravimetry
Process of crystal growth: nucleation and
particle growth
Von Weimarn ratio
Gravimetric calculations

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 Essential elements are reported on the label
in the format NPK
Example: If fertilizer has label 161203, it
means that it has 16% N, 12% P2O5, 3% K2O
(dry basis)
N promotes leaf growth
P promotes root growth
K promotes flowering and fruiting

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 Dissolve fertilizer sample in d H2O
Filter; obtain clear filtrate
+ 10% MgSO47H2O
+ 2 M NH3 (slowly with constant stirring)
Stand for 15 min
Filter; obtain precipitate
Wash with d H2O, then with 95% EtOH
Dry and weigh precipitate

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 Precipitation
Filtration
Drying and/or ignition
Weighing

How do we apply these in our experiment?

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 Phosphorus precipitated as MgNH4PO46H2O
Precipitation reaction:
Mg2+(aq) + NH4+(aq) + HPO42(aq) + OH(aq) + 5H2O(l)
MgNH4PO46H2O(s)
Why in weakly basic conditions?
Source of Mg2+: MgSO47H2O
Source of NH4+: NH3 (Is NH4Cl possible?)

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 Precipitate must be large and filterable
Use of dilute solutions
Slow addition of precipitating reagent
Constant stirring
Use of elevated temperatures (not done in this
experiment)
Digestion

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 Slow addition of NH3 with constant stirring
To produce large and filterable crystals (how?)
Digestion
Letting the precipitate stand in its mother liquor
for some time
Improves purity of precipitate
Removes weakly bound water (i.e. non-essential
water)

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 Washing with 95% EtOH after d H2O
To prevent peptization
For easier removal during drying
Precipitate is dried at 11oC to remove non-
essential water
Sources of error?

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Given the following data for the moisture &
phosphorus determination in fertilizer:
Sample weight (as received): 3.0281 g
Sample weight (dried): 2.9269 g
Weight of precipitate: 0.3466 g
Calculate the following:
1. % moisture
2. % P (30.97 g/mol) and % P2O5 (141.94 g/mol)
MgNH4PO46H2O = 245.41 g/mol
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Chem 28.1
 Analytical methods based on determination
of quantity of a reagent of known
concentration that is required to react
completely with the analyte
Most commonly involves measurement of
volume of the reactant of known
concentration (volumetric titrimetry)

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 Standard a solution of known
concentration
Titrant the reagent that is added to the
analyte solution; usually a standard
Analyte the substance that is to be
determined in a titrimetric analysis
Standardization a process in which the
concentration of a solution is accurately
determined
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 Primary standard a compound of high
purity that serves as reference material for a
titrimetric analysis
Secondary standard a compound whose
purity has been established by chemical
analysis and that serves as reference material
for a titrimetric analysis

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 Equivalence point a theoretical point at
which stoichiometric equivalence between
analyte and titrant is achieved
End point a point at which a physical
change associated with chemical equivalence
occurs
Titration error difference between the
equivalence point and end point
Et = Vep Veq
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 There must be a known reaction between
analyte and titrant
Reaction between analyte and titrant must
be complete and quantitative (Keq 107)
Reaction must be fast
There must be a way to determine the end
point of the reaction

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 Most commonly through indicators
substances that physically change (usually
change in color) upon appearance of excess
titrant
Can also be through instruments:
colorimeters, turbidimeters, voltmeters,
potentiometers, refractometers, etc.

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 Highly pure
Stable in the atmosphere
No water of hydration
Modest cost
Reasonably soluble in titration medium
High molar mass

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 Acid-base or neutralization titration
Precipitation titration
Complexometric titration
Redox titration

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 Millimole approach the mole relationship
of analyte and titrant in the balanced
chemical equation must be known
aA + tT products
# mmol A = (a/t) # mmol T
Milliequivalent approach the number of
equivalents of analyte and titrant are equal
regardless of their mole relationship
# meq A = # meq T
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 Example 1: Calculate the mass of NaHCO3
(84.007 g/mol) that is neutralized by 14.53 mL
of 0.1059 M H2SO4 solution.
Example 2: Calculate the molarity of a 20.00-
mL H2C2O4 solution that needs 21.49 mL of
0.0398 M KMnO4 to reach the end point.
Example 3: Calculate the % KCN (65.116
g/mol) of a 0.1029-g sample if its titration
required 8.12 mL of 0.0472 N AgNO3.
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Chem 28.1 Experiment No. 4
 Crude Na2CO3
Commercial neutralizing agent
Raw material for glass manufacture
Water softener
May contain traces of NaHCO3 or NaOH

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 A soda ash mixture can contain NaOH,
NaHCO3, Na2CO3, or a compatible mixture
of these
The composition can be determined by
titration with an acid using two indicators:
phenolphthalein and methyl orange
Note: It cannot contain a mixture of NaOH
and NaHCO3

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 Titration of carbonate involves 2 equiv. pts.:
(1) CO32 + H3O+ HCO3 + H2O
(2) HCO3 + H3O+ H2CO3 + H2O CO2 + 2 H2O
Overall reaction:
CO32 + 2 H3O+ CO2(g) + 3 H2O
Two distinct endpoints could be observed
(Note that for CO32, Kb1 = 2.13 104 and Kb2
= 2.25 108)

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 First equivalence point: Bicarbonate is the
dominant species; pH of solution?
Phenolphthalein (pH range 8.3 10.0)
Second equivalence point: Carbonic acid is
formed; pH of solution?
Methyl orange (pH range 3.1 4.4)
Bromocresol green (pH range 3.8 5.4)

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http://www.chemguide.co.uk/physical/acidbaseeqia/carbtitinds.gif
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 Component(s) Relationship of V1 Millimoles of
and V2 substance
NaOH V2 = 0 MV1
NaHCO3 V1 = 0 MV2
Na2CO3 V1 = V2 MV1
NaOH + Na2CO3 V1 > V2 NaOH: M(V1 V2)
Na2CO3: MV2
NaHCO3 + Na2CO3 V1 < V2 NaHCO3: M(V2 V1)
Na2CO3: MV1
V1 = volume of titrant needed to reach phenolphthalein end point
V2 = additional volume of titrant needed to reach methyl orange end point
M = molarity of standard HCl (titrant)
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 Solution preparation
Standardization of HCl
Titration of soda ash sample
Titrate with HCl to phenolphthalein endpoint
Titrate until near orange
Boil the solution until yellow again
Titrate again until orange (methyl orange
endpoint)

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 Mixture of NaHCO3 + NaOH is incompatible
They can react: HCO3 + OH CO32 + H2O
Sample contains approximately 20% Na2CO3
+ 30% NaHCO3

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 Use of boiled distilled water
To avoid carbonate error, in which CO2 could
react with NaOH:
CO2 + 2 NaOH Na2CO3 + H2O
The effective concentration of NaOH is reduced
CO2 is removed by boiling
Use of plastic instead of glass for storing
basic solutions
OH reacts with silicates in glass
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 Use of NaOH as primary standard for acids
Not possible since it is hygroscopic, unstable and
has low MW (recall properties of an ideal 1 std.)
We use Na2CO3 instead of NaOH
Boiling before methyl orange endpoint
The end point is not very sharp due to the
H2CO3/HCO3 buffer system
Boiling removes CO2 so the pH will increase,
making the end point sharper
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Chem 28.1 Experiment No. 5
 Active component of aspirin
Has analgesic, anti-inflammatory and
antipyretic properties

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 Mole ratio of ASA to NaOH?
Reaction is hastened by heat

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 A process in which the excess of a standard
solution used to consume an analyte is
determined by titration with a second
standard solution
Done when reaction with analyte is slow
Here, the unreacted NaOH standard solution
is back-titrated by standard HCl solution

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 Standardization of NaOH and HCl
Dissolution of aspirin
+ 1.0 M NaOH
Simmering for 20 min
Dilution & aliquoting
Titrate the aliquot with HCl

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 Standardization of NaOH: 1 standard =
KHP
Standardization of HCl: 1 standard =
Na2CO3
Base hydrolysis of ASA: excess NaOH
standard is reacted with ASA
# mmol ASA = (# mmol NaOH reacted)
Back-titration of NaOH: unreacted NaOH is
titrated with HCl
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 1.0 M NaOH
Primary standard = KHP
Indicator = phenolphthalein
Diluted to o.o5o M prior to standardization
If we use the 1.0 M NaOH solution, the
equivalence point is more rapidly approached
(more moles of base per drop of titrant)
Chances of overtitration are greater

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 0.050 M HCl
Primary standard = Na2CO3
Indicator = methyl orange or phenolphthalein

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 1.0 M NaOH is added to ASA solution
ASA solution is simmered for 20 min
To hasten the reaction between ASA and NaOH
Should not boil off in order to ensure that the all
species involved are in solution

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 Simmered solution is diluted to 250 mL
A 50-mL aliquot of the diluted solution is
then titrated with 0.050 M HCl
For practical reasons: effect on amount of titrant?
Useful if only limited sample is available and
several replicates/trials must be made
To easily repeat the titration when overtitrated

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 Indicator = phenolphthalein
Color change?
Excess NaOH is titrated; can be related to
amount of ASA
Sources of error?

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Chem 28.1 Experiment No. 7
 A measure of the capacity of cations in water
to replace Na+ or K+ in soaps forming
sparingly soluble salts
Can be taken essentially as the
concentration of CaCO3 (ppm CaCO3)
Can be determined using EDTA titration

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Water Hardness ppm CaCO3
soft < 17.1
moderately soft 17.1 60
moderately hard 60 120
hard 120 180
very hard > 180

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 Abbreviated EDTA or H4Y
A tetraprotic, hexadentate chelating agent

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 Commonly used as chelating agent for
various applications:
Chelation therapy
Sequestration or scavenging of metals
Complexometric titration of many metal ions

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 Most common type of complexometric or
complex-formation titration
Used for quantitative determination of most
metal ions (except alkali metal cations)
EDTA chelates metal ions in a 1:1 mole ratio
regardless of the charge of the cation

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 Adjustment of pH enhances selectivity of
EDTA
e.g. trivalent cations at pH 1
Relative stability of complex at a certain pH
Use of auxiliary complexing agents to
selectively form a highly stable complex with
interfering ions

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 If metal ion is Ca2+, the titration reaction is:
Ca2+ + Y4- CaY2-
Millimole relationship?
Standardization of EDTA: 1 standard =
CaCO3
Indicator = eriochrome black T (EBT)
MgCl26H2O: to ensure a sharper endpoint
when Ca2+ is titrated with EDTA

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 Preparation of solutions
Standardization of EDTA
Titration of water sample with EDTA

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 Standard EDTA solution
Na2EDTA2H2O is dissolved in water
Heating and/or addition of NaOH pellets may be
done to improve solubility
NaOH improves solubility:
H2Y2 + 2 OH Y4 + 2 H2O
MgCl26H2O is added to provide a sharper
endpoint

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 NH3/NH4+ buffer
From concentrated NH3 and solid NH4Cl
Should be at pH 10.0 to maintain pH
EBT indicator
Solvent = ethanol
CaCO3 stock standard solution
Dissolved by adding hydrochloric acid
Should not be over-acidified (why?)

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 Use of EBT as indicator
Pertinent titration reactions
During titration:
Ca2+ + HY3 CaY2 + H+
Mg2+ + HY3 MgY2 + H+
At the endpoint:
HY3 + MgIn MgY2 + HIn2 + H+

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 Use of pH 10 for titration of Ca2+ and Mg2+
Concept of conditional formation constant
Form of EDTA at pH 10?
pH 10 = minimum pH for titration of Ca2+ and Mg2+
Why not lower or higher pH?

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 NH3 as auxiliary complexing agent?
It does not act as such since Ca and Mg
hydroxides do not precipitate at pH 10
If Zn2+ was titrated, NH3 could act as auxiliary
complexing agent since Zn(OH)2 may ppt
Zn2+ + 4 NH3 Zn(NH3)42+
Zn(NH3)42+ + HY3 ZnY2 + 3 NH3 + NH4+
What happens when too much buffer is used?
Ca(OH)2 and Mg(OH)2 may ppt less sharp
endpoint
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 In order of decreasing stability:
Complex CaY2 MgY2 MgIn CaIn

Kf 5.0 1010 4.9 108 1.0 107 2.5 105

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 Stoichiometric equation:
# mmol CaCO3 = # mmol EDTA
CaCO3 titer of EDTA:
T = MEDTA FWCaCO3 = NEDTA EWCaCO3
ppm CaCO3 (mg CaCO3/L) in sample:
ppm CaCO3 = (T VmL, EDTA)/(VL, sample)
Sources of error?

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