Course Name: Atomic Spectroscopy

Instructor: Sir Umer Younas

Submitted By: Asad Tariq

Title: Hydride generation (HG) and cold vapor (CV)

technique

M.Sc Chemistry III (Weekend)

Introduction
Hydride generation (HG) is a very effective analytical technique developed to
separate hydride forming metals, such as Se and As, from a range of matrices and varying acid
concentrations. Mercury can be easily reduced in solution to generate elemental mercury,
otherwise known as cold vapor (CV).

The mechanism of volatile hydride generation (HG) and the formation of analyte atoms in the
quartz cell atomizer used in the determination of hydride-forming elements (As, Bi, Ge, Pb, Sb,
Sn, Te etc.) by atomic absorption spectrometry (AAS), have been critically reviewed. The
nascent hydrogen mechanism failed to explain hydride generation under different experimental
conditions when tetrahydroborate (THB), amineboreanes (AB) and cyanotrihydroborate (CBH)
were used as reductants. Various experimental evidence suggested a non-nascent hydrogen
mechanism, in which the transfer of hydrogen directly bonded to boron to an analyte takes place.
In electrochemical hydride generation (EcHG), the reduction of the analyte species and
subsequent hydrogenation was proposed. The mechanism of analyte atom formation in a quartz
tube atomizer has been explained by the following hypotheses: thermal decomposition, oxidation
by 02 and collisions by hydrogen free radicals. The free-radical mechanism satisfactorily
explains most of the analytical implications. The significant variation in the experimental
conditions required to generate different analyte hydrides makes it difficult to arrive at a
generalized mechanism of hydride formation.

Cold Vapor Atomic Absorption Analysis (CVAAS)

The cold vapor method is only used for the determination of mercury. A reaction to produce the
mercury vapor is first carried out in a vessel external to the atomic absorption instrument.
Free mercury atoms can exist at room temperature and can be analysed using atomic
absorption without employing flame and graphite furnace techniques at high temperatures.
Furthurmore, the vapor is monatomic and unreactive and can be taken up in a gas stream
and be measured by atomic absorption as a cold vapor.

One of the most popular methods of Hg analysis is the conversion of Hg salts to Hg vapor by
using a strong acidic reducing agent such as Tin (SnCl2) and HCl or NaBH4 and HCl :

3H2;O + 2NaBH4 + HCl 8H + 2H3BO3

8H + Hg+2 Hg0 + 3H2

Mercury is reduced in solution using stannous chloride or sodium borohydride in a closed
system. The reaction quantitatively releases mercury (from the sample solution) and is carried by
a stream of air, nitrogen or argon through a quartz absorption cell placed in the light path of an
AA instrument for analysis.The detection limit for mercury by this cold vapor technique is
approximately 0.02 mg/L.

HYDRIDE GENERATION - HGAAS

Introduction
Hydride generation sampling systems are similar to cold vapor mercury systems, except that the
hydrides generated must be heated in air/acetylene flame or electrically to create atoms in the
free state.Samples are diluted and acidified, then reduced with a hydride source such as sodium
borohydride in an external system.
Volatile hydride generation (HG) combined with atomic absorption spectrometric (AAS)
determination is a sensitive analytical method for the elements As, Bi, Ge, Pb, Sb, Sn and Te.
The basic design of a hydride generation system with subsequent detection by atomic absorption
may be classified as four steps.
 (1) generation of the hydride;

(2) collection of the hydride (if necessary);

(3) transfer of the hydride to the atomizer;

(4)decomposition of the hydride to the gasphase elemental form within the optical axis of the
detection system.

Generation of Volatile Hydrides

Various reducing agents and sources of nascent hydrogen hav been suggested in order to convert
the element to its hydride. These include Zn/HCl, SnCl2/HCl–KI, Mg/HCl–TiCl3 and THB.47 The
reactions leading to the formation of hydrides with metal/acid reductant can be written as:

Zn + 2H3O+ Zn2+ + 2H2O + 2H·,

Am+ + (m + n)H· AHn + mH+,

where Am+ is an analyte

THB is a particularly versatile reagent, which has become widely used for its reducing and
hydride transfer properties. Assuming the evolution of nascent hydrogen from the acid
hydrolysis of THB, the generation of hydrides is represented as

NaBH4+3H2O+HClH3BO3 +NaCl+8H+ Am+ AHn+H


studies supporting the non-nascent hydrogen hypothesis propose that the hydride is formed by
the action of hydrogen bonded directly to boron through the formation of some hydroboron
intermediates. According to this, the derivatization process may be written as
THB + H3O+ + 2H2O Intermediates H3BO3 + H2

THB/Intermediates + Analyte Hydride

Hydrides have also been generated electrochemically (EcHG). In EcHG the hydride is formed
in the cathodicspace of an electrolytic cell; and the process is considered to take place in at least
two sequential events

Am+ + me– A0

The formation of the hydride from the deposited metal/metalloid

A0 + nH· AHn

where H represent the hydrogen atom, from the adsorbed H atom, reduced H3O+ or reduced H2O.
Role of pH in hydride generation
The role played by the hydrogen ion concentration in analytical HG is two fold. First, it activates
the analyte substrate to suitable chemical form; second, the hydrolysis of THB. A theoretical
modeling and experimental study of As5+ and As3+ indicate that both reactions are pH dependent.
However, As5+ reduction occurs in a lower pH region, which is restricted mainly by the
dissociation of the borohydride. Only a little dissociation of BH4 is necessary for As3+ hydride
generation.

The nebulizer required in AAS is not used in HGAAS. Continuous flow system or batch flow
systems can be used. Acid contents of samples and standards of 10% to 50% are common; this is
much much higher than in normal AAS.

NEW INSTRUMENTS
Simple manual systems as above are still used today, but modern CVASS instruments are
automated and more sensitive, smaller, faster, and less expensive than the AA spectrophotometer
with cold vapor attachments. Today's CVASS systems can give detection limits in parts per
trillion and analyze samples in just about one minute. They require very little operator
interaction, and occupy a minimum of bench space. Modern instruments can measure parts per
million levels of Arsenic, Selenium, Antimony, Bismuth and Tellurium. Detection levels are in
the range of 10ppt and 2ppt for Selenium.

With autosampling and computer controlled software, there is no need for external mixing of
reagents, corrosive acids or or strong oxidizing and reducing agents.

Applications
Applications of both vapor generation techniques have been widespread in that waters and
effluents, metallurgical, clinical, biological, agricultural, geological, and environmental samples
have all been analyzed at both the trace and ultratrace levels for these analytes.