Based on measurement of weight of an analyte or compound containing the analyte.

2 types of method
Precipitation Methods

Based on isolation of an insoluble

precipitate of known composition,

Volatilization Methods.

Analyte is volatilized, weighed and the

is determined.
Refer to notes from : http://www.csudh.edu/oliver/che230/textbook/Grav03.htm

Gravimetric analysis
Calculations associated with the method are based on stoichiometry. The weight has relationship with the analyte and the material used or actually weight

Need to know or refresh few things...

Empirical Formula simplest whole number ratio of

atoms in a compound. Chemical Formula actual of atoms in a compound Molecular Formula gives connectivity

Stoichiometry of Reaction
A balanced formula gives the ratios, in moles of

materials produced or consumed in a reaction.

2NaI (aq) + Pb(NO3)(aq)

PbI2(s) + 2NaNO3(aq)

If the weight of anyone species used or produced is

known, the others are readily calculated.

How much Pb(NO3)2 is need to convert 5.0 grams of

NaI to PbI?
FW Pb(NO3)2 - 3311.2 g/mol, NaI 149.9 g/mol

5.0

Gravimetric calculations are simple an extension of

stoichiometric calculations.
Our stoichiometric factor is most often based on the

amount (in moles) of our analyte in the material actually weighed.

Gravimetric Factor, GF
GF = FW of subs.sought FW of subs.weight x a (mol sought) b (mol weighed)

Sought (g) = weight (g) of pptt x GF

Example
Calculate the weight of barium and the weight of Cl present in 15.0 g BaCl2. Solution GF Ba = 137.30 g/mol x 1 = 0.66 208.20 g/mol 1 Weight of Ba = 15.0 g BaCl2 x 0.66 = _____g Ba

GF of Cl = 35.45 g/mol 208.20 g/mol

x 2 = 0.34 1

Weight of Cl = 15.0 g BaCl2 x 0.17 = _____g Cl

How to determine analyte in a sample?

Sample (contains analyte) Weighing sample Convert to measureable form (pure precipitate) weight of analyte (through GF) % analyte (g analyte/g sample x 100)

Determination of phospate in an organic sample

= 0.2660 g

Now, we ready to do the calculations. Formula weight P = 30.97 g/mol, Mg2P2O7 = 222.6 g/mol
GF = FW of P x 2 = 0.2783

FW of Mg2P2O7

%P
=

= ______

Exercise:
1. Zinc is determined by precipitating and weighing as Zn2Fe(CN)6. a) What weigh of zinc is contained in a sample that gives 0.348 g precipitate? b) What weight of precipitate would be formed from 0.500g of zinc?
Ar Zn = 91.224 g/mol, Zn2Fe(CN)6 = 388.40 g/mol

2. An iron ore is analyzed for iron content by dissolving in acid, converting the iron to Fe2+, and then titrating with standard 0.0150 M K2Cr2O7 solution. If 35.6 mL is required to titrate the iron in a 1.68 g ore sample, how much iron is in the sample, expressed as percent Fe2O3?

Properties of precipitates
To obtain good results, we must be able to produce

pure precipitate that can be recovered with high efficiency.

Criteria of Good precipitate Have low solubility Be easy to recover by filtration Be unreactive to air, water Be something where our analyte is only a small portion of the ppt.

Type of suspension and filterability

Colloidal
Size range : 10-6 10-4 mm Tendency to settle : NO Filterability : Difficult or impossible Purity: Not Pure

Crystalline
10-1 10 mm Will settle spontaneously Readily filtered

Typically higher purity than colloids.

The factors govern the particles size of a precipitate

Precipitate solubility
Temperature Reactant concentration, The rate at which reactants are mixed. The net effect of these variables can be accounted for,

at least qualitatively, by assuming that the particle size is related to a single property of the sytem called its relatuve supersaturation, RSS where

Competing process in during Precipitation

Several steps must be taken to help precipitate a

colloid and reduce impurities.

Any steps taken must address two competing process

which are
Coagulation Process where colloid particles lump

together into larger particle. Peptization Process when a coagulated colloid reverts to its dispersed state.

Coagulation of Colloids
Two common approaches for causing a colloid to

coagulate are
Heating Adding an eelctrolyte to the solution.

Addressing Peptization
If trouble to making a coagulate colloid our attempt

is to clean it up.
Washing a colloid to remove excess counter ion or

trapped impureties can result in peptization.

There are several common approaches that can be

used to address this problem

Treatment of Colloid Precipitates

Use a volatile electrolyte Digestion

Aging

Type of Coprecipitation and How to dealing with.

1. Surface adsorption 2. Mixed Crystal Surface of the precipitate will Formation
content some primary absorbed ions. As a result, a counter ions will also be present. Worse for colloid, Why? How to deal Washing (may help but not much) Washing with volatile electrolyte Reprecipitation
If similar ions are present, they

can replace an analyte ion in the crystal lattice during precipitation. Similar ions have the same charge and sizes within 5% of the ion. How to deal No easy solution to minimize the problem. Try to remove the interference or select a different reagent.

3. Occlusion
If crystal growth is too rapid,

4. Entrapment
When rapid growth traps a

some counter ion dont have time to escape from the surface

pocket of a solution. While the solvent can be removed, the trapped ions will remain after drying.

How to deal Slow things down Using dilute and warm solution Digestion and Aging