Voltammetry

Voltammetry
An Introduction in Theory
Metrohm Ltd. CH-9100 Herisau Switzerland

Overview

Voltammetry

What is Voltammetry? Electrode Types Voltammetric Techniques Measurement Modes Calibration Techniques Advantages of Voltammetry Summary

Voltammetry

Voltammetry

Voltammetry = Volt-Am(pero)-Metry Voltage ramp applied to electrode Current measured

I = f(U)

Method first described 1922 by Heyrovsky

Instrumentation in voltammetry

Voltammetry

Me+
746

e-

Me0

Voltage Source (Potentiostat)

polarographic cell

Principle of voltammetry

Voltammetry

Pb ions are reduced and dissolved in mercury

+
Pb2+ Pb2+ Pb2+ Pb2+ Pb2+ Pb2+ Pb2+

Pb2+

Pb2+ Pb2+ Pb2+ +2ePb0 Pb2+ Pb2+ Pb2+

Pb2+

Pb2+

Pb2+

Principle of voltammetry

Voltammetry

resulting curve

I
quantitative information

U qualitative information

Principle of voltammetry

Voltammetry

U Pb I Cd

potential increased current measured metal ions are reduced and dissolved in mercury.

time

Reduction to metal (amalgam formation)

Electrodes

Voltammetry

1 1 1

Working Electrode Reference Electrode Auxiliary Electrode

Reference electrode

Voltammetry

provides stable reference potential

Ag/AgCl/KCl 3 mol/L
Double junction system with exchangeable electrolyte

Auxiliary electrode

Voltammetry

Current flows between working and auxiliary electrode Two types available:

Platinum (Pt) Glassy Carbon (GC)

Depending on application !

Working Electrodes

Voltammetry

MME
Multi Mode Electrode

RDE
Rotating Disc Electrode

GC, Au, Ag Pt, UT SMDE DME HMDE

MME

Voltammetry

Multi Mode Electrode

mercury needle tapper

capillary
Hg drop

Multi Mode Electrode

Voltammetry

DME

Needle

SMDE

HMDE

Tapper

Capillary

Hg drop

New Drop

Stable surface

One drop !

Droplife

Choice of the working electrode

Voltammetry

Depends on the concentration of the analyte DME SMDE HMDE & RDE

Traces

ppm

Low ppm

ppb

ppt

Which working electrode ?

Voltammetry

Standard electrode: MME Organics: DME or SMDE Metal Traces: HMDE Special applications: RDE Gold electrode: Hg, As UT* with Hg film: Cd, Pb, Cu UT* Hg free: Cr, W, Ni
* UT: Ultra Trace Graphite Electrode

Which working electrode ?

Voltammetry

Potential ranges of different electrode types

Oxidation of electrode

Mercury Glassy Carbon

Gold

H+ + e-

Platinum Potential (V) -1.2 -1.0 -0.8 -0.6 -0.4 -0.2 0 0.2 0.4 0.6 0.8 1 1.2

Voltammetric Techniques

Voltammetry

Polarography

uses the dropping mercury electrode (DME, SMDE)

(Stripping) Voltammetry

uses a stationary electrode (HMDE, RDE)

Voltammetric Analysis

Voltammetry

Polarography

Pb2+

Pb0

direct reduction or oxidation at the electrode limited sensitivity universal technique

Voltammetric Techniques

Voltammetry

Polarography

Stripping Voltammetry
U

U Pb I Cd

Pb I Cd

time

Electrolysis time

Reduction to metal (amalgam formation)

Reduction to metal (amalgam formation)

Oxidation to ion (determination)

Voltammetric Analysis

Voltammetry

Anodic Stripping Voltammetry (ASV) 2 steps

1. deposition (metal reduction) Cd2+ Cd0(Hg) 2. determination (Stripping) Cd0(Hg) Cd2+

2 steps
CSV

Voltammetric Analysis

Voltammetry

Adsorptive Stripping Voltammetry (AdSV)

1. deposition (adsorption) Ni2+(DMG-)2

Ni2+(DMG-)2ads

2. determination (Stripping) Ni2+(DMG-)2ads Ni2+ +

2 DMGred

DMG: Dimethylglyoxime, complexing agent

Stripping Voltammetry

Voltammetry

Properties

2 step measurement electrochemical deposition (enrichment) determination (stripping step) high sensitivity for trace analysis (down to ppt range) mainly for metal analysis.

PSA

Measurement Modes

Voltammetry

= modulation of potential ramp

Purpose:

Increasing sensitvity decreasing background signals Increasing selectivity separation of faradayic and capacitive current

Direct Current: DC

Voltammetry

potential ramp
U

resulting curve

time

voltage step

wave height
drop time time

half wave potential

Differential Pulse: DP

Voltammetry

potential modulation

resulting curve
I

U pulse amplitude drop time voltage step time

peak height peak potential

DC and DP

Voltammetry

I
quantitative information

U I
quantitative information

U qualitative information

U
Modes

Electrolyte in VA

Voltammetry

Correct electrolyte is most important :

see Application Bulletins

Purpose of the electrolyte:

Increases the conductivity Adjusts the pH Complexes the analyte Increase selectivity (masking of interfering elements)

Electrolyte in VA

Voltammetry

Peak potentials of different metals depending on the electrolyte

NH4Ac/HAc NH3/NH4Cl Mn Mn Co

Co

Ni Zn

Cd Cd CdPb

Pb Pb Cu Hg

Cu

Hg

Hg Hg Hg

Zn Co Ni Zn

Na tartrate Potential (V)

CuHg 0

-1.6 -1.4 -1.2 -1.0 -0.8 -0.6 -0.4 -0.2

0.2 0.4 0.6

Concentration evaluation

Voltammetry

Peak evaluation Calibration

standard addition external calibration (calibration curve)

Peak evaluation

Voltammetry

height

Peak maximum Basepoints Baseline Peak height Peak area

basepoints

baseline

Calibration Curve

Voltammetry

Voltammograms of standards

Calibration Curve

peak height

conc c1 c2 c3

Sample with Cal. Curve

Voltammetry

Voltammograms of sample

Calibration Curve

peak height

conc c sample

Standard Addition

Voltammetry

Voltammograms additions

Standard Addition Curve

peak height

conc -cS Add1 Add2

sample

E
Sum

Calibration Techniques

Voltammetry

External Calibration

Measure standard solutions Calculate calibration curve measure sample

Standard Addition

measure sample measure additions to sample solution

Voltammetry

Why Voltammetry?

Advantages of Voltammetry

Voltammetry

No problem with high salt concentrations Speciation possible: e.g. Cr3+ - Cr6+ free / complexed metal Low detection limits: sub-ppb Capital outlay: Low price Low running costs: only N2

Advantages of Voltammetry

Voltammetry

No extensive laboratory infrastructure Versatility: inorganics and organics Anions Official methods (DIN,ISO,USP, ASTM, etc.) Alternative and complementary method to AAS/ICP

Advantages of Voltammetry

Voltammetry

Simultaneous Determination of Metals: up to 4 metals in one run Automation: 80 Samples plus all buffers and standards Calibration in every run: Variable Standard Addition if required.

Summary

Voltammetry

Most important points

What you should know about VA !

Voltammetry

VA: Voltam[pero]metry

I = f(U) AE: Pt, GC RE: Ag/AgCl/KCl 3 mol/L WE: MME (DME, SMDE, HMDE) or RDE DC, DP, AC1/AC2, SQW, CV, PSA

Electrodes:

Measurement Modes:

What you should know about VA !

Voltammetry

Methods

Polarography: "Liquid" electrode (DME, SMDE) Stripping Voltammetry (HMDE, RDE): Anodic Stripping Voltammetry Adsorptive Cathodic Stripping Voltammetry Allows signal enhancement Increase selectivity Allows masking of elements

Electrolyte (buffer)

What you should know about VA !

Voltammetry

Concentration Evaluation:

Peak evaluation Calibration Standard Addition Technique Calibration Curve Technique

Advantages of Voltammetry