Reaction rate

Reaction rate (rate of reaction) or speed of reaction for a reactant or product in a particular reaction is intuitively defined as how fast or slow a reaction takes place. For example, oxidative rusting of iron under atmosphere is a slow reaction that can take many years, but combustion of cellulose in a fire is a reaction that takes place in fractions of a second. Chemical kinetics is part of physical chemistry that studies reaction rates. Concepts of chemical kinetics are applied in many disciplines, such as chemical engineering, enzymology&environmental engineering.

Contents
1. 2. 3. 4. 5. 6. Formal definition of reaction rate Factors influencing rate of reaction Rate equation Temperature dependence Pressure dependence Example: Reaction of hydrogen and nitric oxide

Formal definition of reaction rate

Consider a typical chemical reaction: aA + bB pP + qQ The lowercase letters (a, b, p, & q) represent stoichiometric coefficients, while capital letters represent reactants (A & B) & products (P & Q). According to IUPAC's Gold Book definition reaction rate r for a chemical reaction occurring in a closed system under isochoric conditions, without a build-up of reaction intermediates, is defined as:

where [X] denotes concentration of substance X. (Note: rate of a reaction is always positive. A negative sign is present to indicate reactant concentration is decreasing.) IUPAC recommends that unit of time should always be second. In such a case rate of reaction differs from rate of increase of concentration of a product P by a constant factor (reciprocal of its stoichiometric number) & for a reactant A by minus reciprocal of stoichiometric number. Reaction rate usually has units of mol L1 s1. It is important to bear in mind that previous definition is only valid for a single reaction, in a closed system of constant volume. This most usually implicit assumption must be stated explicitly, otherwise definition is incorrect: If water is added to a pot containing salty water, concentration of salt decreases, although there is no chemical reaction. For any system in general full mass balance must be taken into account: In-Out + Generation -Consumption= Accumulation

When applied to closed system at constant volume considered previously, this equation reduces to: . Here , where concentration is the Avogadro constant. is related to number of molecules by

For a single reaction in a closed system of varying volume so-called rate of conversion can be used, in order to avoid handling concentrations. It is defined as derivative of extent of reaction with respect to time.

Here is stoichiometric coefficient for substance , equal to a, b, p, & q in typical reaction above. Also is volume of reaction & is concentration of substance . When side products or reaction intermediates are formed, IUPAC recommends use of terms rate of appearance & rate of disappearance for products & reactants, properly. Reaction rates may also be defined on a basis that is not volume of reactor. When a catalyst is used reaction rate may be stated on a catalyst weight (mol g 1 s1) or surface area (mol m2 s1) basis. If basis is a specific catalyst site that may be rigorously counted by a specified method, rate is given in units of s1 & is called a turnover frequency.

Factors influencing rate of reaction

Nature of reaction: Some reactions are naturally faster than others. Number of reacting species, their physical state (particles that form solids move much more slowly than those of gases or those in solution), complexity of reaction&other factors can greatly influence rate of a reaction. Concentration: Reaction rate increases with concentration, as described by rate law & explained by collision theory. As reactant concentration increases, frequency of collision increases. Pressure: rate of gaseous reactions increases with pressure, which is, in fact, equivalent to an increase in concentration of gas. Reaction rate increases in direction where there are fewer moles of gas &decreases inreverse direction. For condensed-phase reactions, pressure dependence is weak. Order: order of reaction controls how reactant concentration (or pressure) affects reaction rate. Temperature: Usually conducting a reaction at a higher temperature delivers more energy into system & increases reaction rate by causing more collisions between particles, as explained by collision theory. However, main reason that temperature increases rate of reaction is that more of colliding particles will have necessary activation energy resulting in more successful collisions (when bonds are formed between reactants). Influence of temperature is described by Arrhenius equation. As a rule of thumb, reaction rates for many reactions double for every 10 degrees Celsius increase in temperature, though effect of temperature may be very much larger or smaller than this.

For example, coal burns in a fireplace in presence of oxygen, but it does not when it is stored at room temperature. Reaction is spontaneous at low & high temperatures but at room temperature its rate is so slow that it is negligible. Increase in temperature, as created by a match, allows reaction to start & then it heats itself, because it is exothermic. That is valid for many other fuels, such as methane, butane, & hydrogen.

Reaction rates can be independent of temperature ( non-Arrhenius) or decrease with increasing temperature (anti-Arrhenius). Reactions without an activation barrier (e.g., some radical reactions), tend to have anti Arrhenius temperature dependence: rate constant decreases with increasing temperature.

Solvent: Many reactions take place in solution and properties of solvent affect reaction rate. Ionic strength also has an effect on reaction rate. Electromagnetic radiation & intensity of light: Electromagnetic radiation is a form of energy. As such, it may speed up rate or even make a reaction spontaneous as it provides particles of reactants with more energy. This energy is in one way or another stored in reacting particles (it may break bonds, promote molecules to electronically or vibrationally excited states...) creating intermediate species that react easily. As intensity of light increases, particles absorb more energy&hence rate of reaction increases.

For example, when methane reacts with chlorine in dark, reaction rate is very slow. It can be sped up when mixture is put under diffused light. In bright sunlight, reaction is explosive.

A catalyst: presence of a catalyst increases reaction rate (in both forward & reverse reactions) by providing an alternative pathway with a lower activation energy.

For example, platinum catalyzes combustion of hydrogen with oxygen at room temperature.

Isotopes: kinetic isotope effect consists in a different reaction rate for same molecule if it has different isotopes, usually hydrogen isotopes, because of mass difference between hydrogen & deuterium. Surface Area: In reactions on surfaces, which take place for example during heterogeneous catalysis, rate of reaction increases as surface area does. That is because more particles of solid are exposed & can be hit by reactant molecules. Stirring: Stirring can have a strong effect on rate of reaction for heterogeneous reactions.

All the factors that affect a reaction rate, except for concentration & reaction order, are taken into account in rate equation of reaction.

Rate equation

For a chemical reaction n A + m B p P + q Q, rate equation or rate law is a mathematical expression used inchemical kinetics to link rate of a reaction to concentration of each reactant. It is of kind: For gas phase reaction rate is often alternatively expressed by partial pressures. In these equations (T) is reaction rate coefficient or rate constant, although it is not really a constant, because it includes all parameters that affect reaction rate, except for concentration, which is explicitly taken into account. Of all parameters influencing reaction rates, temperature is normally the most important one & is accounted for by Arrhenius equation. Exponents n & m are called reaction orders and depend on reaction mechanism. Stoichiometry, molecularity (actual number of molecules colliding), & reaction order coincide necessarily only in elementary reactions, that is, those reactions that take place in just one step. Reaction equation for elementary reactions coincides with process taking place at molecular level, i.e. molecule A collides with molecule B. From collision theory follows that likelihood of a collision of three molecules is highly unlikely. Therefore molecularity for elementary reactions is either one or two. Empirically, other values can be assigned to allow mathematical description of rate. Then, positive rational numbers are not uncommon but should not be assigned physical meaning.

By using mass balance for system in which reaction occurs, an expression for rate of change in concentration can be derived. For a closed system with constant volume, such an expression can look like

Temperature dependence

Each reaction rate coefficient k has a temperature dependency, which is usually given by Arrhenius equation: Ea is activation energy & R is gas constant. Since at temperature T molecules have energies given by a Boltzmann distribution, one can expect number of collisions with energy greater than Ea to be proportional to . A is pre-exponential factor or frequency factor. Values for A & Ea are dependent on reaction. There are also more complex equations possible, which describe temperature dependence of other rate constants that do not follow this pattern. A chemical reaction takes place only when reacting molecules collide. However, not all collisions are effective in causing reaction. Products are formed only when colliding molecules possess a certain minimum energy called threshold energy. Basically, number of activated molecules nearly doubles for a temperature T+10K. Ratio of a reaction at a given temperature to its rate constant at a temperature 10o lower is called temperature coefficient.

Pressure dependence

Pressure dependence of rate constant for condensed-phase reactions (i.e., when reactants & products are solids or liquid) is usually sufficiently weak in range of pressures normally encountered in industry that it is neglected in practice. Pressure dependence of rate constant is associated with activation volume. For reaction proceeding through an activation-state complex: Activation volume, where , is:

denote partial molar volumes of reactants & products & indicates activation-state complex.

For above reaction, one can expect change of reaction rate constant (based either on molefraction or on molar-concentration) with pressure at constant temperature to be:

In practice, matter can be complicated because partial molar volumes & activation volume can themselves be a function of pressure. Reactions can increase or decrease their rates with pressure, depending on value of . As an example of possible magnitude of pressure effect, some organic reactions were shown to double reaction rate when pressure was increased from atmospheric (0.1-50MPa (which gives =-0.025 L/mol).

Example: Reaction of hydrogen and nitric oxide

For reaction

Observed rate equation (or rate expression) is:

As for many reactions, rate equation does not simply reflect stoichiometric coefficients in overall reaction: It is third order overall: first order in H2 & second order in NO, although stoichiometric coefficients of both reactants are equal to 2. In chemical kinetics, overall reaction rate is often explained using a mechanism consisting of a number of elementary steps. Not all of these steps affect rate of reaction; normally the slowest elementary step controls reaction rate. For this example, a possible mechanism is: 1. 2. 3. (fast equilibrium) (slow) (fast)

Reactions 1 & 3 are very rapid compared to second, so slow reaction 2 is rate determining step. This is a bimolecular elementary reaction whose rate is given by second order equation: , where k2 is rate constant for second step. However N2O2 is an unstable intermediate whose concentration is determined by fact that first step is in equilibrium, so that: , where K1 is equilibrium constant of the first step. Substitution of this equation in the previous equation leads to a rate equation expressed in terms of original reactants

This agrees with form of observed rate equation if it is assumed that . In practice rate equation is used to suggest possible mechanisms which predict a rate equation in agreement with experiment.

Rate equation
Rate law or rate equation for a chemical reaction is an equation that links reaction rate with concentrations or pressures of reactants & constant parameters (normally rate coefficients & partial reaction orders). To determine rate equation for a particular system one combines reaction rate with a mass balance for system. For a generic reaction aA + bB C with no intermediate steps in its reaction mechanism (that is, an elementary reaction), rate is given by

where [A] & [B] express concentration of species A & B, respectively (usually in moles per liter (molarity, M)); x & y must be determined experimentally (a common mistake is assuming they represent stochiometric coefficients but this is not case). k is rate coefficient or rate constant of reaction. Value of this coefficient k depends on conditions such as temperature, ionic strength, surface area of adsorbent or light irradiation. For elementary reactions, rate equation can be derived from first principles using collision theory. Again, x&y are not always derived from balanced equation.

Rate equation of a reaction with a multi-step mechanism cannot, in general, be deduced from stoichiometric coefficients of overall reaction; it must be determined experimentally. Equation may involve fractional exponential coefficients, or it may depend on concentration of an intermediate species. Rate equation is a differential equation, & it can be integrated to obtain an integrated rate equation that links concentrations of reactants or products with time. If concentration of one of reactants remains constant (because it is a catalyst or it is in great excess with respect to other reactants), its concentration can be grouped with rate constant, obtaining a pseudo constant: If B is reactant whose concentration is constant, then . second-order rate equation has been reduced to a pseudo-firstorder rate equation. This makes treatment to obtain an integrated rate equation much easier.

Contents
1. 2. 3.

1Stoichiometric reaction networks Zero-order reactions First-order reactions Further Properties of First-Order Reaction Kinetics Second-order reactions Pseudo-first-order Summary for reaction orders 0, 1, 2, and n Equilibrium reactions or opposed reactions Simple Example Generalization of Simple Example Consecutive reactions Parallel or competitive reactions General Dynamics of Unimolecular Conversion

4. 5. 6.

7. 8. 9.

Stoichiometric reaction networks

The most general description of a chemical reaction network considers a number of distinct chemical species reacting via reactions. chemical equation of -th reaction can then be written in generic form

which is often written in equivalent form

Here
is the reaction index running from 1 to denotes the -th chemical species, is the rate constant of the -th reaction and ,

and

are the stoichiometric coefficients of reactants and products, respectively.

The rate of such reaction can be inferred by the law of mass action

which denotes flux of molecules per unit time & unit volume. Here vector of concentrations. Note that this definition includes elementary reactions:
zero-order reactions for which first-order reactions for which second-order reactions for which for exactly two a dimerization reaction. , i.e, a bimolecular reaction, or for a single for a single , for all ,

is

, i.e.,

Each of which are discussed in detail below. One can define the stoichiometric matrix

denoting the net extend of molecules of in reaction be written in the general form

. The reaction rate equations can then

Note that this is product of stochiometric matrix & vector of reaction rate functions. Particular simple solutions exist in equilibrium, , for systems composed of merely reversible reactions. In this case rate of forward and backward reactions are equal, a principle called detailed balance. Note that detailed balance is a property of stoichiometric matrix alone & does not depend on particular form of rate functions . All other cases where detailed balance is violated are commonly studied by flux balance analysis which has been developed to understand metabolic pathways.

Zero-order reactions
A Zero-order reaction has a rate that is independent of concentration of reactant(s). Increasing concentration of reacting species will not speed up rate of reaction i.e. amount of substance reacted is proportional to time. Zero-order reactions are typically found when a

material that is required for reaction to proceed, such as a surface or a catalyst, is saturated by reactants. Rate law for a zero-order reaction is

where r is reaction rate & k is reaction rate coefficient with units of concentration/time. If, and only if, this zeroth-order reaction 1) occurs in a closed system, 2) there is no net build-up of intermediates, & 3) there are no other reactions occurring, it can be shown by solving a mass balance equation for system that:

If this differential equation is integrated it gives an equation often called the integrated zeroorder rate law.

where

represents the concentration of the chemical of interest at a particular time, and

represents the initial concentration. A reaction is zero order if concentration data are plotted versus time and the result is a straight line. A plot of vs. time t gives a straight line with a slope of .

The half-life of a reaction describes the time needed for half of the reactant to be depleted (same as the half-life involved in nuclear decay, which is a first-order reaction). For a zeroorder reaction the half-life is given by

Example of a zero-order reaction

Reversed Haber process:

It should be noted that order of a reaction cannot be deduced from chemical equation of the reaction.

First-order reactions
A first-order reaction depends on concentration of only one reactant (a unimolecular reaction). Other reactants can be present, but each will be zero-order. rate law for a reaction that is first order with respect to a reactant A is

k is the first order rate constant, which has units of 1/s.

The integrated first-order rate law is

A plot of

vs. time t gives a straight line with a slope of

half-life of a first-order reaction is independent of starting concentration and is given by . Examples of reactions that are first-order with respect to the reactant:

Further Properties of First-Order Reaction Kinetics

The integrated first-order rate law

is usually written in the form of the exponential decay equation

A different (but equivalent) way of considering first order kinetics is as follows: exponential decay equation can be rewritten as:

where corresponds to a specific time period and is an integer corresponding to number of time periods. At end of each time period, fraction of reactant population remaining relative to amount present at the start of the time period, , will be:

Such that after

time periods, the fraction of the original reactant population will be:

where: corresponds to fraction of reactant population that will break down in each time period. This equation indicates that fraction of total amount of reactant population that will break down in each time period is independent of initial amount present. When chosen time

period corresponds to , fraction of population that will break down in each time period will be exactly amount present at start of time period (i.e. time period corresponds to half-life of first-order reaction). The average rate of the reaction for the nth time period is given by:

Therefore, amount remaining at end of each time period will be related to average rate of that time period & reactant population at start of the time period by:

Since fraction of reactant population that will break down in each time period can be expressed as:

The amount of reactant that will break down in each time period can be related to the average rate over that time period by:

Such that amount that remains at end of each time period will be related to amount present at start of the time period according to:

This equation is a recursion allowing for calculation of amount present after any number of time periods, without need of rate constant, provided that average rate for each time period is known.

Second-order reactions
A second-order reaction depends on concentrations of one second-order reactant, or two first-order reactants. For a second order reaction, its reaction rate is given by:

or

or

In several popular kinetics books, the definition of rate law for second-order reactions is written instead as . This effectively conflates the 2 inside constant, k, whose numerical meaning then becomes different. This simplifying convention is followed in integrated rate laws provided below. It should be noted however that this simplification leads to potentially problematic inconsistencies, i.e. if reaction rate is described in terms of product formation vs reactant disappearance. Instead, option of keeping 2 in rate law (rather than absorbing it into a rate constant with an altered meaning) maintains a consistent meaning for k & is considered more correct technically. This more technically consistent convention is almost always used in peer-reviewed literature, tables of rate constants, & simulation software Integrated second-order rate laws are respectively

or

[A]0 & [B]0 must be different to obtain that integrated equation. Half-life equation for a second-order reaction dependent on one second-order reactant is . For such a reaction, half-life progressively doubles as concentration of reactant falls to half its initial value. Another way to present above rate laws is to take log of both sides:
Examples of a Second-order reaction

Pseudo-first-order

Measuring a second-order reaction rate with reactants A & B can be problematic: concentrations of two reactants must be followed simultaneously, which is more difficult; or measure one of them & calculate other as a difference, which is less precise. A common solution for that problem is the pseudo-first-order approximation If either [A] or [B] remains constant as reaction proceeds, then reaction can be considered pseudo-first-order because, in fact, it depends on concentration of only one reactant. If, for example, [B] remains constant, then:

where (k' or kobs with units s1) & an expression is obtained identical to the first order expression above. One way to obtain a pseudo-first-order reaction is to use a large excess of one of reactants ([B]>>[A]) would work for previous example) so that, as reaction progresses, only a small amount of reactant is consumed, & its concentration can be considered to stay constant. By collecting for many reactions with different (but excess) concentrations of [B], a plot of versus [B] gives (regular second order rate constant) as slope. Example: The hydrolysis of esters by dilute mineral acids follows pseudo-first-order kinetics where concentration of water is present in large excess.
CH3COOCH3 + H2O CH3COOH + CH3OH

Summary for reaction orders 0, 1, 2, & n

Elementary reaction steps with order 3 (called ternary reactions) are rare & unlikely to occur. However, overall reactions composed of several elementary steps can, of course, be of any (including non-integer) order.
Rate Law Zero-Order First-Order Second-Order nth-Order

Integrated Rate Law Units of Rate Constant (k) Linear Plot to determine k Half-life

[8]

[8]

[Except first order]

[Except first order]

[8]

[Except first order]

Where M stands for concentration in molarity (mol L1), t for time, & k for reaction rate constant. Half-life of a first-order reaction is often expressed as t1/2 = 0.693/k (as ln2 = 0.693).

Equilibrium reactions or opposed reactions

A pair of forward & reverse reactions may define an equilibrium process. For example, A & B react into X & Y & vice versa (s, t, u, & v are stoichiometric coefficients):

Reaction rate expression for above reactions (assuming each one is elementary) can be expressed as:

where: k1 is rate coefficient for reaction that consumes A & B; k2 is rate coefficient for backwards reaction, which consumes X & Y & produces A & B. Constants k1 & k2 are related to equilibrium coefficient for reaction (K) by following relationship (set r=0 in balance):

Concentration of A (A0 = 0.25 mole/l) & B versus time reaching equilibrium kf = 2 min-1 & kr = 1 min-1 Simple Example

In a simple equilibrium between two species:

Where reactions starts with an initial concentration of A, 0 for B at time t=0. Then constant K at equilibrium is expressed as:

, with an initial concentration of

Where

&

are concentrations of A & B at equilibrium, respectively. , is related to concentration of B at time t, , by

Concentration of A at time t, equilibrium reaction equation:

Note that term

is not present because, in this simple example, initial concentration of B is 0.

This applies even when time t is at infinity; i.e., equilibrium has been reached:

then it follows, by definition of K, that

and, therefore,

These equations allow us to uncouple system of differential equations, & allow us to solve for concentration of A alone. Reaction equation, given previously as:

Derivative is negative because this is rate of reaction going from A to B, & therefore concentration of A is decreasing. To simplify annotation, let x be time t. Let be concentration of A at equilibrium. Then: , concentration of A at

Since:

Reaction rate becomes:

which results in:

A plot of negative natural logarithm of concentration of A in time minus concentration at equilibrium versus time t gives a straight line with slope kf + kb. By measurement of Ae & Be values of K & two reaction rate constants will be known.[9]
Generalization of Simple Example

If concentration at time t = 0 is different from above, simplifications above are invalid, & a system of differential equations must be solved. However, this system can also be solved exactly to yield following generalized expressions:

When equilibrium constant is close to unity & reaction rates very fast for instance in conformational analysis of molecules, other methods are required for determination of rate constants for instance by complete lineshape analysis in NMR spectroscopy.

Consecutive reactions
If rate constants for following reaction are & ; , then rate equation is:

For reactant A:

For reactant B:

For product C: With individual concentrations scaled by total population of reactants to become probabilities, linear systems of differential equations such as these can be formulated as a master equation. Differential equations can be solved analytically & integrated rate equations are

The steady state approximation leads to very similar results in an easier way.

Parallel or competitive reactions

When a substance reacts simultaneously to give two different products, a parallel or competitive reaction is said to take place.

Two first order reactions:

& and integrated rate

, with constants

&

& rate equations

equations and

are

then .

One important relationship in this case is One first order and one second order reaction:[ This can be case when studying a bimolecular reaction & a simultaneous hydrolysis (which can be treated as pseudo order one) takes place: hydrolysis complicates study of reaction kinetics, because some reactant is being "spent" in a parallel reaction. For example A reacts with R to give our product C, but meanwhile hydrolysis reaction takes away an amount of A to give B, a by-product: & . Rate equations are: &

Where

is pseudo first order constant.

Integrated rate equation for main product [C] is , which is equivalent to .

Concentration of B is related to that of C through Integrated equations were analytically obtained but during process it was assumed that Therefore, previous equation for [C] can only be used for lowconcentrations of [C] compared to [A]0 General Dynamics of Unimolecular Conversion For a general unimolecular reaction involving inter-conversion of different species, whose concentrations at time are denoted by through , an analytic form for timeevolution of species can be found. Let rate constant of conversion from species to species be denoted as Also, let , and construct a rate-constant matrix whose entries are . be vector of concentrations as a function of time.

Let be vector of ones. Let be identity matrix. Let be function that takes a vector and constructs a diagonal matrix whose on-diagonal entries are those of vector. Let be inverse Laplace transform from to . Then time-evolved state is given by , Thus providing relation between initial conditions of the system and its state at time .