Chapt 4- NTLP

GRAVIMETRIC ANALYSIS

Application to Food Analysis

CONTENTS
 History of Gravimetric Analysis
 Gravimetric techniques
 Direct gravimetric analysis
 Indirect gravimetric analysis
 Precipitate gravimetric analysis
 Others
 Gravimetric analysis procedure
 Data calculations
 Application to food analysis

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 Chapt 4- NTLP

History of Gravimetric Analysis

 Jons Jacob Berzelius (1779-1848)
 Use of ashless filter paper in gravimetry
 Use of hydrofluoric acid (HF) to decompose silicates
 Use of the metric system in weight determinations
 Theodore W. Richards (1868-1928)
 Developed and refined many techniques of
gravimetric analysis of silver and chlorine to
determine the atomic weights.
 Nobel Prize in Chemistry in 1914

Gravimetric analysis
 Gravimetric methods based on determining the mass of
a pure compound to which the analyte is chemically
related.
 an absolute measurement (accurate and precise methods)
Example:

 Determination of lead (Pb+2) in water

Pb+ + 2Cl-  PbCl2(s)

 By adding excess Cl- to the sample, essentially all of the Pb+2 will
precipitate as PbCl2.

 Mass of PbCl2 is then determined.

- used to calculate the amount of Pb+2 in original solution

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 Chapt 4- NTLP

Classification of Gravimetric methods

 Volatilization gravimetry
 Ash analysis
 Water analysis
 Precipitation methods
 Inorganics
 Organics
 Miscellaneous methods
 Electro-gravimetry

Direct gravimetric analysis

 Ashing analysis – Chapter 16 (287- 297)
 Ash refers to the inorganic (mineral) residue
remaining after the combustion or complete
acid-facilitated oxidation of organic matter in
food.
 first step in mineral analysis
 02 major types: dry ashing and wet ashing.
 The final (ashed) weight is compared to the
original weight of the sample.

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Ashing analysis
 Dry ashing
 Wet ashing
 Ash content (total mineral):
0 - 12 %
(< 5 % for fresh foods)

The average ash content

for various food groups

Ashing analysis
 METHODS
 Principles,
 materials,
 instrumentation,
 general procedures,
 and applications

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Ashing analysis
 Sample Preparation
- Sample sizes: 2–10 g even 250 mg (newer
instruments)
- a homogenous, representative sample
- use of sample blanks
 Source of contaminants:
 Eliminate of contaminants

Ashing analysis –
Sample preparation
 Plant Materials
 - oven-dried (remove moisture) in two stages:
first at a lower temperature of 55 °C, then at a
higher temperature ≤ 100 °C. Plant material with
moisture ≤ 15 % ashed without prior drying.
 - the goal of the analysis is ash or specific
mineral analysis alone, low-temperature drying
and then ashed in the same crucible.
 Fat and Sugar Products
 Animal products, syrups, and spices (high fat,
moisture, or high sugar content)

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Ashing analysis
 Dry Ashing
 Principles and Instrumentation
 ≥ 525 °C
 Crucible selection
 Quartz crucibles
 Vycor® brand crucibles
 Pyrex® Gooch crucibles
 Porcelain crucibles
 Steel crucibles
 Platinum crucibles
 Quartz fiber crucibles

Ashing analysis
 Dry Ashing
 Calculations
 The ash content:

 WAA = weight after ashing

 TWOC = tare weight of crucible
 OSW = original sample weight
 DMC = % solids/100

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Ashing analysis
 Wet Ashing
 Principle, Materials, and Applications
 Wet ashing/ wet oxidation/ wet digestion.
 acid solutions:
 (1) nitric acid,
 (2) sulfuric acid-hydrogen peroxide
 (3) perchloric acid
 AOAC procedure (e.g., AOAC Method 975.03)
 A combination of dry and wet ash procedure:
AOAC Method 985.35

Ashing analysis
 Microwave Ashing
 wet ashing and dry ashing
 Closed-vessel microwave digestion systems
 Open-vessel digestion systems

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Ashing analysis
 Microwave Dry Ashing
 microwave muffle furnaces

Ashing analysis
 Other Ash Measurements
 1. Soluble and insoluble ash (e.g., AOAC
Method 900.02).
 2. Ash insoluble in acid.
 3. Alkalinity of ash (e.g., AOAC Method
900.02, 940.26).
 4. Sulfated ash (AOAC Method 900.02,
950.77).

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 Chapt 4- NTLP

Volatilization gravimetry
Moisture analysis
 Water content (Moisture content)
 Water activity
 Importance of Moisture Assays
 Preservation and stability
 Quality factors
 Convenience in packaging or shipping
 Meeting compositional standards and standards of identity
 Accurate computation of nutritional value
 Expressing results of other analytical determinations on a
uniform basis

Water in Foods

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Moisture analysis
 Oven Drying Methods
 Forced Draft Oven
 Vacuum Oven
 Microwave Analyzer
 Infrared Drying
 Rapid Moisture Analyzer Technology
 Thermogravimetric Analyzer
 Distillation

Moisture analysis
 Oven Drying Methods
 direct methods
 the sample is heated under specified conditions,
and the loss of weight is used to calculate the
moisture content of the sample.
 The amount of moisture determined is highly
dependent on the type of oven used, conditions
within the oven, and the time and temperature of
drying.
 Time required: ~1 h - >24 h.

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Moisture analysis
 Removal of Moisture
 Decomposition of Other Food Constituents
 Temperature Control
 Types of Pans for Oven Drying Methods
 Handling and Preparation of Pans
 Calculations
 wwb
 dwb

Precipitation analysis
 The quantitative determination of a substance by
precipitation followed by isolation and weighing of the
precipitate.
X (analyte) + C (reagent)  CX (sparingly soluble)
 Example:
 Determination of Calcium in natural water
AOAC (Association of Official Analytical Chemists)

2NH 3  H 2 C 2 O 4  2NH 4  C 2 O 24-

Ca 2 (aq )  C 2 O 24- (aq )  CaC 2 O 4 ( s )
To
CaC 2 O 4 ( s )  CaO(s)  CO (s)  CO 2 

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Common Steps in Gravimetric analysis

1. Sampling
2. Preparation of the solution
3. Precipitation
4. Digestion
5. Filtration
6. Washing
7. Drying or igniting
8. Weighing
9. Calculation

Weigh precipitate

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Precipitating agents
 Produce a precipitate of low solubility product,
Ksp
 Specifically: react only with a single species
 Eg. Dimethylglyoxime  Ni2+
 Selectively: react with a limited number of
species
 Eg. AgNO3  Cl-, Br-, I-, SCN-

Relative supersaturation (RS) ratio

QS
RS 
S
 Q – concentration of the solute at any instant
 S – equilibrium solubility
 Particle size is in inverse ratio to RS (# 1/RS)

RS  particle size  (colloidal)

RS  particle size  (crystalline solid)

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Solubility Product (S)

BmAn (solid) BmAn (soln.) m Bx+ + n Ay-

Sparingly soluble almost complete dissociation since the resulting
electrolyte substance soln. is very dilute
(having ionic lattice)

Solubility = s moles/L B  = ms moles/L A  = ns moles/L

x y

B  A 
x m y n But, [BmAn] is constant because the soln is
in contact with large excess of solid BmAn
Ke =
Bm An  Ke X [BmAn] = S (Solubility product )

S=B   A 
x m y n
= (ms)m (ns)n

DATA CALCULATIONS
 Sample in solid form

 Sample in liquid form

 Gravimetric factor (F)

= ×

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Data calculation
 Solid sample
1. Weighing a (g) of solid sample, obtaining m (g) of
weighed precipitate (compound or mixture):
m
%X  .100
a

Data calculation
 Solid sample
 Convert from mass of dried pure precipitate to mass
of analyte (X)

MX 100
%X  m    mole ratio 
M ppt a

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Data calculation
 Solid sample
1. Weighing a (g) of solid sample, diluted into V (mL), get
VX (mL) obtaining m (g) of weighed precipitate
(compound or mixture):

V 100
%X  m   
VX a

Data calculation
 Liquid sample
1. VX mL of liquid sample  gravimetric analysis  m (g)
dried precipitate
MX 1000
Cg / L ( X )  m    mole ratio 
M ppt VX

2. V mL of sample diluted into V1 (mL), get VX (mL)

obtaining m (g) of weighed precipitate:

V1 1000
C g / L ( X )  m  .F . .
VX V

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