Food Analysis

Determination of
Salt in Food

Titration
Ion Selective
Electrodes
Density
Balances

The Ultimate Salt Guide

Proven Analytical Methods and Results
Salt and humans go a long way together. In earlier times, before mining of rock salt had
started, salt was a high-priced and much sought after commodity. Nowadays, with cheaper
salt prices, salt is a key ingredient in processed foods. This guide will:

Give insights into methods of salt determination in food

Provide a short overview of the history of salt
Show and explain measurement in selected samples
Present a few tips and hints to improve operator technique on titrators and balances.

Content 2

1. Introduction 3
2. Solutions Overview 4
3. Argentometric Titration 4
4. Ion Selective Methods 5
5. Determination of Salt Content Based on Density 7
6. Ash Content 8
7. Conclusions 9
8. More Information 9
9. Appendix 9
Ti-Note 17 10
Ti-Note 12 12
Ti-Note 19 14

METTLERTOLEDO Salt Guide 2

1. Introduction

Salt From White Gold to Commodity

Salt has a long standing culture and can be traced back to ancient times in most civilizations. Babylonians and
Sumerians have used salt for conservation of food items. Salt was always in high demand and rare in many
regions. Because of salt, many cities have become rich and influential, for instance Luneburg within the Hanse
region.

No wonder that salt has been called 'the white gold'. Interestingly though, even the word salary originates from
the original meaning of a 'soldier's allowance for salt'. Salt was especially high-priced in the Middle Ages and
became affordable in the Germanophone regions only when harvesting the several 100 meters thick, about 250
million year old, salt layers of the Zechsteinmeer in Northern Germany, was made possible.

Table salt, consisting mainly of sodium chloride, is the most commonly used salt in our food. Even after the
production process of customary table salt, either from rock salt or sea salt, 1-3% of other salts are remaining;
unprocessed sea salt contains up to 5% of water. Table salt is a cleaned and refined salt. To improve attributes
such as pourability and hygroscopy, small amounts of other substances are later on added to the salt. In table
salt, sea salt and stone salt are often distinguished. Both are harvested in different processes

Rock Salt
Rock salt is often a product that is mined from underground. Harvesting is assured either through digging the
rock salt out or by solving out. Table salt is then separated from other substances in salines, through selected
solving and concentrating and then condensation or boiling.

Different cultures around the globe have developed different techniques to harvest salt. Some South American
Indian tribes gain a potassium chloride rich salt from leeching plant ash. In the area around the Chad Lake,
earth containing salt is leeched, filtered and then boiled down. In earlier times, in some areas of Northern
Germany, peat which had been flooded by the sea was utilized to extract salt.

Sea Salt
Harvesting salt from sea water is probably the oldest method of harvesting salt. Sea water is channeled into
salt gardens, where the water slowly evaporates. All dissolved ions, depending on their solubilities, crystallize
one after another in different layers. Sodium chloride is in the top layer that is harvested before the water entirely
evaporates. Contamination with other salts cannot be prevented in this way of salt harvesting, however often is
a marketing feature when sold. Nowadays about 20% of the global consumption of salt is extracted from sea
water.

Salt Today
Salt is an essential ingredient of processed food and the salt content of products often needs to be determined
as accurately as possible. Considering the past glory of the 'white gold', salt nowadays often has something of a
bad reputation. Too much of it mainly sodium ion has adverse effects on our health. Currently WHO and FAO
have taken initiatives that aim at capping the salt consumption by defining maximum values for food products.
It is expected that this trend will continue and maximum admissible values of salt content will come into place.
Pressure on the food manufacturers to reduce the salt content in their products is likely to increase. Thus, many
recipes have undergone reformulation or are still waiting to be reworked. Such tasks require quite a lot of testing
including salt content determination.

The following sections will give insights into the different methods of salt determination, e.g. titration, loss on
drying, then give insights into the determination of the salt content in selected food items and finally offer some
tips and hints on how to improve measurement techniques for easier working procedures and more accurate
results.

METTLERTOLEDO Salt Guide 3

2. Solutions Overview

Salt Content Determination in Solid and Liquid Samples

Several techniques for the determination of salt, chloride, sodium and potassium in almost any kind of samples
are available at METTLER TOLEDO. Liquid samples may undergo direct determination. Solid samples however,
may require a preparation step to release the salt and dissolve the ions.

Titration Ion selective Density Analytical Precision

methods Balance Balance

Salt content
Chloride content
Sodium content
Potassium content
Ash content (total salts)

3. Argentometric Titration of Salt

Titration
Titration is one of the oldest chemical quantitative analyses. Still today, this very reliable method of high
accuracy and precision is well appreciated and frequently applied. Its linearity, i.e. whether a certain method
produces correct results over the concentration range of interest, is unsurpassed. Hence, very low up to very
high concentrations are safely determined. For the calibration of the method, simply the titer determination is
carried out.

Argentometry
A very common method of the salt content determination is the argentometric titration of the chloride ion. Based
on the chloride content, the amount of sodium chloride, i.e. salt, is then calculated.
The argentometric titration is a precipitation reaction: The sparingly soluble silver chloride is formed from the
chloride ions contained in the sample and the added silver nitrate of the titrant.
Ag+ + Cl- AgCl

With precipitation titrations, several characteristics should be noted.

The titration reaction may be slower compared e.g. with an acid/base titration in aqueous samples. Thus,
apply a medium titration speed as referenced in many METTLER TOLEDO applications.
At the start of the titration, the sample solution may become supersaturated before the precipitate is formed.
Hence, the electrode cannot indicate the proceeding of the titration reaction. In order to avoid super saturation,
we recommend adjusting the pH of the sample solution to the required value. For the chloride titration in
general, the sample solution is slightly acidified with nitric acid to 4.5 pH.
With highly concentrated sample solutions, inclusions of sample and/or titrant may occur in the precipitate,
thereby falsifying the result. Rapid stirring during titration is an effective countermeasure.

Results
Sample Mean RSD % n
Mustard (low salt) 0.142% 1.19 8
Tomato juice 0.50% 0.13 5
Ham pie 1.69% 3.12 6
Ketchup 2.67% 0.17 15
Seasoning 17.24% 0.18 8
Mixed spices 55.66% 0.18 6

METTLERTOLEDO Salt Guide 4

4. Ion Selective Methods

Ion Selective Electrodes

Ion selective electrodes (ISE) are an alternative method to measure the concentration of ions in solutions. It is a
simple setup consisting of the respective ISE, a suitable ion meter, titrator or similar instrument and a stirrer. An
ISE is built of a sensing element, a membrane, and the electrode body. There are 4 types of sensing membranes
in use for the various ISEs.

Type Application examples

Glass membrane pH, sodium
Crystalline membrane (solid state) Fluoride, iodide, cupper
Polymer membrane (liquid membrane) Potassium, calcium, lithium
Gas sensing Dissolved oxygen, carbon dioxide

Types of membranes

Measurement
The ISE responses to the concentration - or more precisely the activity - of the determinant ion. The response
follows the Nernst equation which is well known from pH measurement. If the influence of interfering ions is
included as well, this equation is extended to the Nicolsky equation.
However, both equations describe a linear relation between the potential readings (in mV) and the logarithm of
the ion concentration (or activity respectively). At the detection limit and in high concentrations, linearity is no
longer achieved and determinations deteriorate. For most ions, the applicable concentration range is specified
from 10-1 to 10-5 mol/L.

Response Time
ISEs reach a stable potential reading typically within 1 to 3 minutes. The response time usually is at the shorter
end in concentrated solutions and at the longer end in diluted solutions respectively.

Storage of the ISE

For short periods of time, it is recommended to store the electrode in 0.01 mol/L standard solution of the
respective ion.
For longer periods, i.e. more than 1 week, store dry. For dry storage see the ISE instructions. In general, drain
electrode and flush with deionized water. Then protect the sensing element.

Interferences
ISEs are selective to one ion but not specific for it. Thus, other ions present in the sample solution also contribute
to the reading of the electrode. The selectivity coefficient describes the preference of the ISE over the interfering
ions. Selectivity coefficients are typical for an ISE and specified in the instruction manual.

METTLERTOLEDO Salt Guide 5

For a 0.001 mol/L potassium solution, the following interferences occur:

Measured ion Potassium K+

Interfering ion Concentration which causes an error Interference
of 10%
Cesium Cs+ 0.0003 mol/L very high
Ammonium NH4+ 0.006 mol/L high
Hydronium H+ 0.01 mol/L low
Sodium Na+ 2.0 mol/L very low

Ionic Strength Adjustment

In order to avoid or keep low the influence of interfering and other ions, ionic strength adjustment buffers (ISAB)
are added to the sample solutions. ISAB is also added to the standard solutions to keep standard and sample
solutions as comparable as possible.
The instruction manual of the ISE specifies which ISAB is recommended.

Some types of ionic strength adjustment buffers

ISE ISAB
Potassium K+
TEACl, NaCl
Calcium Ca2+ KCl, NaCl
Fluoride F- Mixture of NaCl, acetic acid, sodium acetate and CDTA
TEACl = tetraethyl ammonium chloride
CDTA = 1,2-cyclohexylene diamine tetraacetic acid

Results Potassium
Sample Mean RSD % n
White wine 764 mg/L 0.20 6
Milk 1557 mg/L 0.36 6
Orange juice 1698 mg/L 0.12 6
Carrot juice 3076 mg/L 0.29 6
Elderberry juice 3739 mg/L 0.17 5

Results Sodium
Sample Mean RSD % n
White wine 8.4 mg/L 0.63 5
Milk 433.8 mg/L 0.20 6
Grape juice 23.8 mg/L 0.66 5
Bouillon 4110 mg/L 0.35 5
Bouillon (salt reduced) 468.5 mg/L 0.35 5

METTLERTOLEDO Salt Guide 6

5. Determination of Salt Content Based on Density

The salt content of a solution made of salt and water (i.e. 2 components only) can also be determined by
density measurements. The more salt is dissolved in the water (or a solvent) the higher is the density. Based on
a conversion table, the salt content is evaluated from the density measurement.

Traditional techniques for the density measurement are hydrometers and pycnometers. However, these methods
are time consuming, need considerable sample volumes and are prone to reading errors.

Sodium chloride, 25C, in water

Salt content g/L 25 20 10 5 1
Density g/cm3 1.1887 1.1478 1.0707 1.0340 1.0053

Density Measurement and Density Meters

Current density meters apply the physical principle of the oscillating U-tube. The oscillation frequency depends
on the mass of the U-tube which is the contents of the U-tube respectively. Thus, a few milliliter of sample are
applied by syringe or an automatic sample changer to the density meter instrument.

Schematic of density cell

The measurement takes 2 - 3 minutes, needs no reagents and allows the sample to be recollected for further
uses.
Rinsing and drying of the U-tube before the next sample can be done automatically. This adds result safety to the
fast speed of the measurement.
Because density depends on temperature, modern density meters are electronically thermostated and
compensate the density results to 20C or any other temperature.

Influence of temperature on the density of water

METTLERTOLEDO Salt Guide 7

Results
Sample Mean value RSD % n
of salt content of density value
Normal saline solution (isotonic) 0.9 % w/w 0.02 12
Salt solution (sodium chloride in deion. water) 9.8 % w/w 0.02 6
Brine 17.9.% w/w <0.02 6

6. Ash Content
Food and food ingredients contain lower or higher amounts of inorganic compounds e.g. sodium chloride. Salts
of organic compounds, e.g. sodium acetate, calcium stearate, are a further source of ions. If the food sample
is ashed, such inorganic compounds remain. Thus, ash is the inorganic residue after organic matter and water
have been removed by the ashing process.

The ash content is a measure for the total amount of mineral salts. However, the ash content is not equal to the
sum of mineral salts because during ashing volatile inorganic compounds are evaporated (= loss of weight) and
oxides or carbonates are formed (= gain of weight).
The determination of the ash content provides information for
Nutritional labeling: The amount of minerals is often requested to be declared.
Processing: The content of minerals can affect the physical and chemical properties of food.

Ashing
Ashing is the procedure of decomposing the sample until mineralization is complete. In food analysis, dry
ashing and wet ashing procedures are applied.

Dry Ashing: In general, the sample is placed in a platinum crucible and heated to 550C in a furnace for
2 3 hours. Water and other volatiles are evaporated. Organic substances are decomposed in the presence
of oxygen (air) to carbon dioxide, water and eventually other small molecules which evaporate completely.
Most minerals are converted to oxides, sulfates or chlorides. The sample weight before and after ashing is
taken. The difference of the 2 weighings is the ash content.
If reagents are added to support the mineralization, the remaining amount of reagents has to be taken into
account.

Wet Ashing: Wet ashing in strong acids and oxidizing reagents is usually applied if further analyses have to
be performed such as the determination of specific minerals or if inorganic compounds have to be deter-
mined which evaporate while heating in the furnace. The sample is weighed into a flask. The remaining liquid
after complete digestion is filled to a defined volume and undergoes further analysis.

Results
Sample Mean
Beef tallow (fat) <0.1%
Milk (whole) 0.67%
Turkey 0.88%
White pepper 1.59%
Yellow mustard 3.64%
Blue cheese 5.11%
Chili powder 11.81%

METTLERTOLEDO Salt Guide 8

7. Conclusions

There are several methods available to determine the salt content of food items. Depending on the consistency
of the sample (liquid vs. solid), legal and labeling requirements, level of accuracy and precision as well as
opportunities of the lab, the most suitable method is selected. Argentometric titration surely is the most accurate
method to determine the salt content and very frequently applied. However, the use of ISEs to determine
selectively sodium or potassium may be needed. Salt content determination via density might prove to be faster
but less accurate.

METTLER TOLEDO supplies food laboratories with the right instruments, for the corresponding method of choice.
Find out more about our products, and get in touch with our experts, for suggestions on how you can benefit
from METTLER TOLEDO's expertise in the food industry.

8. More Information

Find more about solutions from METTLER TOLEDO

More about potentiometric titrators: www.mt.com/titration

More about density meters: www.mt.com/Liquiphysics
More about Excellence balances: www.mt.com/excellence

If you liked this guide, we are proudly presenting the METTLER TOLEDO series of guides for the food industry.
Please click on the below links to get access to the respective food guides.

The Ultimate Sugar Guide www.mt.com/sugar-lab

The Ultimate Acidity Guide www.mt.com/acidity-lab
The Ultimate Formulation Guide www.mt.com/formulation-lab
The Ultimate Edible Fats and Oils Guide www.mt.com/fat-lab
The Ultimate Moisture and Water Content Guide www.mt.com/moisture-lab

9. Appendix

Ti-Note 17 Chloride Content in Ketchup

Ti-Note 12 Potassium Content Detemination by Direct Measurement
Ti-Note 19 Sodium Determinationwith ISE

METTLERTOLEDO Salt Guide 9

METTLERTOLEDO Salt Guide 10
METTLERTOLEDO Salt Guide 11
METTLERTOLEDO Salt Guide 12
METTLERTOLEDO Salt Guide 13
METTLERTOLEDO Salt Guide 14
METTLERTOLEDO Salt Guide 15
Good Measuring Practices
Five Steps to Improved Measuring Results

Good Measuring Practices by METTLER TOLEDO is a global program sup-

porting you in laboratory and production environments with quality assur-
ance measures for balances, scales, pipettes and analytical instruments.
The five steps of all Good Measuring Practices guidelines start with an
evaluation of the measuring needs of your processes and their associated
risks. We also take into account regulatory requirements and norms
relevant to your industry.
With this information, Good Measuring Practices provide straight forward
recommendations for selecting, installing, calibrating and operating of
weighing and measuring instruments.

www.mt.com/gwp for weighing

www.mt.com/gtp for titration
www.mt.com/gpp for pipetting
www.mt.com/gdrp for density and refractometry

5
Routine 1
Operation Evaluation

Good
Measuring
4
Calibration / Practices 2
Qualication Selection

3
Installation /
Training

www.mt.com
For more information

Mettler-Toledo AG
Laboratory Division
Im Langacher
CH-8606 Greifensee, Switzerland

Subject to technical changes

09/2012 Mettler-Toledo AG
Global MarCom Switzerland