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The Arrhenius Equation Is A Simple
The Arrhenius Equation Is A Simple
The Arrhenius Equation Is A Simple
more correctly, of a rate coefficient, as this coefficient includes all magnitudes that affect reaction rate except for concentration.[1] The equation was first proposed by the Dutch chemist J. H. van 't Hoff in 1884; five years later in 1889, the Swedish chemist Svante Arrhenius provided a physical justification and interpretation for it. Nowadays it is best seen as an empirical relationship.[2]
Overview
In short, the Arrhenius equation is an expression that shows the dependence of the rate constant k of chemical reactions on the temperature T (in Kelvin) and activation energy Ea, as shown below:.[3] . where A is the pre-exponential factor or simply the prefactor and R is the gas constant. The units of the pre-exponential factor are identical to those of the rate constant and will vary depending on the order of the reaction. If the reaction is first order it has the units s-1, and for that reason it is often called the frequency factor or attempt frequency of the reaction. When the activation energy is given in molecular units, instead of molar units, e.g. joules per molecule instead of joules per mol, the Boltzmann constant is used instead of the gas constant. It can be seen that either increasing the temperature or decreasing the activation energy (for example through the use of catalysts) will result in an increase in rate of reaction. Given the small temperature range in which kinetic studies are carried, it is reasonable to approximate the activation energy as being independent of temperature. Similarly, under a wide range of practical conditions, the weak temperature dependence of the preexponential factor is negligible compared to the temperature dependence of the factor; except in the case of "barrierless" diffusion-limited reactions, in which case the pre-exponential factor is dominant and is directly observable. Some authors define a modified Arrhenius equation,[4] that makes explicit the temperature dependence of the pre-exponential factor. If one allows arbitrary temperature dependence of the prefactor, the Arrhenius description becomes overcomplete, and the inverse problem (i.e. determining the prefactor and activation energy from experimental data) becomes singular. It has been pointed out that "it is not feasible to establish, on the basis of temperature studies of the rate constant, whether the predicted T dependence of the pre-exponential factor is observed experimentally".[2].. but if additional evidence is available, from theory and/or from experiment (such as density dependence), there is no obstacle to incisive tests of the Arrhenius law. Taking the natural logarithm of the Arrhenius equation yields:
. So, when a reaction has a rate constant which obeys the Arrhenius equation, a plot of ln(k) versus T -1 gives a straight line, whose slope and intercept can be used to determine Ea and A. This procedure has become so common in experimental chemical kinetics that practitioners have taken to using it to define the activation energy for a reaction. That is the activation energy is defined to be (-R) times the slope of a plot of ln(k) vs. (1/T):
where G is the Gibbs free energy of activation, kB is Boltzmann's constant, and h is Planck's constant. At first sight this looks like an exponential multiplied by a factor that is linear in temperature. However, one must remember that free energy is itself a temperature dependent quantity. The free energy of activation includes an entropy term, which is multiplied by the absolute temperature, as well as an enthalpy term. Both of them depend on temperature, and when all of the details are worked out one ends up with an expression that again takes the form of an Arrhenius exponential multiplied by a slowly varying function of T. The precise form of the temperature dependence depends upon the reaction, and can be calculated using formulas from statistical mechanics involving the partition functions of the reactants and of the activated complex. The Arrhenius equation
What the various symbols mean Starting with the easy ones . . . Temperature, T To fit into the equation, this has to be meaured in kelvin. The gas constant, R This is a constant which comes from an equation, pV=nRT, which relates the pressure, volume and temperature of a particular number of moles of gas. It turns up in all sorts of unlikely places!
Activation energy, EA This is the minimum energy needed for the reaction to occur. To fit this into the equation, it has to be expressed in joules per mole - not in kJ mol-1.
Note: If you aren't sure about activation energy, you should read the introductory page on rates of reaction before you go on. Use the BACK button on your browser to return to this page.
And then the rather trickier ones . . . e This has a value of 2.71828 . . . and is a mathematical number, a bit like pi. You don't need to worry exactly what it means, although if you have to do calculations with the Arrhenius equation, you may have to find it on your calculator. You should find an ex button - probably on the same key as "ln". The expression, e-(EA / RT) For reasons that are beyond the scope of any course at this level, this expression counts the fraction of the molecules present in a gas which have energies equal to or in excess of activation energy at a particular temperature. You will find a simple calculation associated with this further down the page. The frequency factor, A You may also find this called the pre-exponential factor or the steric factor. A is a term which includes factors like the frequency of collisions and their orientation. It varies slightly with temperature, although not much. It is often taken as constant across small temperature ranges. By this time you've probably forgotten what the original Arrhenius equation looked like! Here it is again:
You may also come across it in a different form created by a mathematical operation on the standard one:
"ln" is a form of logarithm. Don't worry about what it means. If you need to use this equation, just find the "ln" button on your calculator.
Using the Arrhenius equation The effect of a change of temperature You can use the Arrhenius equation to show the effect of a change of temperature on the rate constant - and therefore on the rate of the reaction. If the rate constant doubles, for example, so also will the rate of the reaction. Look back at the rate equation at the top of this page if you aren't sure why that is. What happens if you increase the temperature by 10C from, say, 20C to 30C (293 K to 303 K)? The frequency factor, A, in the equation is approximately constant for such a small temperature change. We need to look at how e-(EA / RT) changes - the fraction of molecules with energies equal to or in excess of the activation energy. Let's assume an activation energy of 50 kJ mol-1. In the equation, we have to write that as 50000 J mol-1. The value of the gas constant, R, is 8.31 J K-1 mol-1. At 20C (293 K) the value of the fraction is:
By raising the temperature just a little bit (to 303 K), this increases:
You can see that the fraction of the molecules able to react has almost doubled by increasing the temperature by 10C. That causes the rate of reaction to almost double. This is the value in the rule-of-thumb often used in simple rate of reaction work.
Note: This approximation (about the rate of a reaction doubling for a 10 degree rise in temperature) only works for reactions with activation energies of about 50 kJ mol-1 fairly close to room temperature. If you can be bothered, use the equation to find out what happens if you increase the temperature from, say 1000 K to 1010 K. Work out the expression -(EA / RT) and then use the ex button on your calculator to finish the job. The rate constant goes on increasing as the temperature goes up, but the rate of increase falls off quite rapidly at higher temperatures.
The effect of a catalyst A catalyst will provide a route for the reaction with a lower activation energy. Suppose in the presence of a catalyst that the activation energy falls to 25 kJ mol-1. Redoing the calculation at 293 K:
If you compare that with the corresponding value where the activation energy was 50 kJ mol-1, you will see that there has been
a massive increase in the fraction of the molecules which are able to react. There are almost 30000 times more molecules which can react in the presence of the catalyst compared to having no catalyst (using our assumptions about the activation energies). It's no wonder catalysts speed up reactions!
Other calculations involving the Arrhenius equation If you have values for the rate of reaction or for the rate constant at different temperatures, you can use these to work out the activation energy of the reaction. Only one UK A' level Exam Board expects you to be able to do these calculations. They are included in my chemistry calculations book, and I can't repeat the material on this site.
L1 - Load Life Rating Vr - Maximum Rated Voltage Vo - Operating Voltage Tm - Max.Temp.Rating of Capacitor TA - Ambient Temp.
Calculate
Film Capacitors
The operating conditions affect the life of a film capacitor in a very similar manner to aluminum electrolytic capacitors. Voltage derating has a greater effect on the life as compared to an aluminum electrolytic capacitor. The life expectancy formula for film capacitors is expressed by the following equation:
L1 - Load Life Rating Vr - Maximum Rated Voltage Vo - Operating Voltage Tm - Max.Temp.Rating of Capacitor Ta - Ambient Temp.
Calculate
Ceramic Capacitors
The life of a ceramic capacitor at the operating conditions is expressed by the following equation:
L1 - Load Life Rating Vr - Maximum Rated Voltage Vo - Operating Voltage Tm - Max.Temp.Rating of Capacitor Ta - Ambient Temp.
Mechanical faults in the electrical insulation system include stress cracking, vibration, mechanical incursion, and mechanical faults. The forces within a coil during various operations, will cause mechanical movement and may end in the fracturing of insulation materials. Electrical and mechanical vibration cause undue stress on the insulation system resulting in stress fractures and looseness of the insulation system. Mechanical incursion includes the movement of materials into the insulation system either between conductors and/or insulation system to ground. Mechanical faults include failures such as bearing faults that cause the bearing to come apart and pass through the moving components of the system. These faults may end as shorts between conductors, coils or coils to ground.