NUR AZAWANEE BINTI MOHD YUSOF (AP073019) 870813085320 NUR ATIKAH BINTI ZULKIFLI (AS100138) 910812145858

SSC 2413 : PHYSICAL CHEMISTRY II

INTRODUCTION

HISTORY

THE EXPERIMENTAL STUDY OF FAST REACTIONS

BACKGROUND

TYPES OF TECHNIQUE AND ITS PRINCIPLE

SSC 2413 : PHYSICAL CHEMISTRY II

One of the important recent developments in chemical kinetics has been interest in the study of very fast reactions which complete in less than about 1 sec. With special laser techniques it is now possible to study the reactions occurring in a few pico seconds (1012sec). For slow reaction (classical method), studying reaction rates is to mix the reactants to start the reaction and then determine the concentration of some reactant or product as a function of time.

This classical method is inadequate to be used if the reaction is comparable to or shorter than the time required to mix the reactants

SSC 2413 : PHYSICAL CHEMISTRY II

The techniques, have been designed to monitor concentrations and

to measure the rate coefficients , to explore the dependence of reaction rate on the state of rotational/ vibrational excitation of molecules or on the energy with which molecules colloid and the rate (state-to-state cross sections and rates) at which the energy is changed from one form into another.

SSC 2413 : PHYSICAL CHEMISTRY II

There are two classes of method to study the fast reaction

Flow Techniques Relaxation Techniques

SSC 2413 : PHYSICAL CHEMISTRY II

FLOW TECHNIQUES
Continuous-flow method Stopped-flow method.

(to speed up the mixing of liquids or gases)

RELAXATION TECNIQUES

(does not rely on mixing but use the fact that equilibrium compositions depend on temperature and sometimes on pressure)

Shock-wave method Flash photolysis method Temperature-jump method Pressure-jump method

SSC 2413 : PHYSICAL CHEMISTRY II

Developed by Strehlowand Becker (1959). for the generation of short-term pressure differences in solution. PRESSURE-JUMP AND TEMPERATURE-JUMP METHOD Was developed in 1923 by Hartridge and Roughton in aid of their study of the kinetics of the reaction between hemoglobin and oxygen.

HISTORY

CONTINUOS-FLOW METHOD

FLASH PHOTOLYSIS METHOD

SHOCK-WAVE METHOD

STOPPED-FLOW METHOD

First developed by Norrish and Porter (1949) only for reactions in the gaseous phase and later transferred to reactions in solutions.

Was published in 1899 by French scientist, Pierre Vieille, to study the flow of fast moving gases over objects, the chemistry and physical dynamics of gas phase combustion reactions.

First described by Chance (1940) and Gibson & Milnes (1964), with a view to probing enzyme kinetics.

SSC 2413 : PHYSICAL CHEMISTRY II

FLOW TECHNIQUES

RELAXATION TECHNIQUES

CONTINUOUSFLOW METHOD

SHOCK-WAVE METHOD STOPPED-FLOW METHOD

TEMPERATURE-JUMP METHOD AND PRESSURE-JUMP METHOD

FLASH PHOTOLYSIS METHOD

SSC 2413 : PHYSICAL CHEMISTRY II

Flow system replace the clock as a timer by a distance along a tube.

Figure 1: Schematic diagram for Continuous-Flow Method

The time for mixing limits the rate of reaction which can be followed. The moment of mixing gives the zero time.
The observation points are at accurately known distance along the tube and larger distances correspond to longer reaction times.

2 gases or 2 solutions are rapidly mixed and flow rapidly along a tube which there are observation chambers at accurately known distances at which the concentration is determined either in situ or by leaking samples. Eg:- if mixing takes 10-3 s, the reactions over in around 10-3 s or less cannot be studied.

SSC 2413 : PHYSICAL CHEMISTRY II

Two reagents are rapidly mixed by being force into a small chamber fitted with a syringe and then through observation cell.

The flow ceases when the plunger of the syringe reaches a stop, and the reaction continues in the mixed solutions.

Figure 2 In the stopped-flow technique the reagents are driven quickly into the mixing chamber by the driving syringes and then the time dependence of the concentrations is monitored.

The change in the spectroscopic signal as a function of time is recorded.

SSC 2413 : PHYSICAL CHEMISTRY II

A shock tube (shown schematically) essentially consists of two chambers separated by a diaphragm. One chamber contains the appropriate mixture of reactants and precursor, the second an inert gas at high pressure. To initiate reaction, the diaphragm is punctured and a shock wave propagates through the reaction mixture. The temperature rise can be controlled by varying the pressure and composition of the inert gas. The composition of the reaction mixture after initiation is monitored in real time, usually spectroscopically.

Diagram of Shock Tube

SSC 2413 : PHYSICAL CHEMISTRY II

The principle of flash photolysis is based on activating a component of the reaction system by a short, very intensive flashlight and then observe the reaction thus initiated. The molecules have to be photosensitive and are transformed into free radicals or into a triplet state. This limits the range of applications to systems possessing such compounds or where such compounds may be inserted. For the generation of flashes discharge flash lamps are used with argon, krypton or xenon fillings. They may achieve time resolutions of a few milliseconds.

Diagram of Flash Photolysis Apparatus

SSC 2413 : PHYSICAL CHEMISTRY II

The reaction mix in the observation chamber is heated by a sudden temperature shock and observed with optical and polarographic techniques. The temperature jump is mostly triggered by discharging a high voltage condenser ove r a spark gap. The electric surge discharge over gold or platinum electrodes through the solution in the observation cell and is then grounded. Ion friction in the electric field induces a rapid temperature in-crease (Joule heating).
Scheme of Temperature Jump method

SSC 2413 : PHYSICAL CHEMISTRY II

The sample is inserted into the cell of an special autoclave, closed by a flexible Teflon membrane and surrounded by a pressure conducting medium (water, paraffin). This is covered with an elastic polyethylene membrane and the remaining space in the autoclave is filled with compressed gas of 5.5 MPa. One opening of the autoclave has been previously closed with a conductive, pressureresistant membrane out of copper beryllium bronze. A magnetic trigger releases the locking device of a metal needle fixed above the membrane. This needle punches the membrane and simultaneously starts recording. The membrane tears under high pressure and pressure in the solution relaxes.

Scheme of Pressure Jump device

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