Name: reaction mechanisms and rate-determining steps
Uploaded: 2023-04-30T18:28:32.000Z
Duration: 2 min 31 s
Channel: JoVE

K12 Standards

Louisiana Student Standards for Science

High School

Chemistry

Matter And Its Interactions

HS-PS1-6

Multi-Step Reactions

Uma reação química é frequentemente representada por uma equação química balanceada geral indicando os reagentes e produtos.
No entanto, a reação real costuma ser mais complexa e ocorre em várias etapas. Por exemplo, essa reação do óxido nítrico com o hidrogênio formando gás nitrogênio e água ocorre em três etapas distintas e sucessivas. Essas etapas são chamadas de mecanismo de reação.
Cada etapa do mecanismo de reação é chamada de reação elementar e representa a interação, como quebra ou formação de ligação, entre as espécies reagentes.
Moléculas específicas, como dióxido de dinitrogênio e óxido nitroso, são formadas durante uma etapa elementar e consumidas durante outra. Essas espécies são chamadas de intermediários de reação.
Os intermediários de reação não são o mesmo que os estados de transição, que existem apenas durante a transformação de reagentes em produtos.
Os mecanismos de reação são hipotetizados com base em suas equações químicas balanceadas e leis de taxa determinadas experimentalmente de cada etapa elementar.
Cada etapa tem uma taxa de reação específica, constante de taxa e energia de ativação. A etapa mais lenta é chamada de etapa de determinação da taxa e influencia a taxa de reação líquida. Ele pode ser usado para verificar a lei de taxa para a reação geral e para validar um mecanismo de reação proposto.
Considere a decomposição do óxido nitroso em nitrogênio e oxigênio. A lei de velocidade determinada experimentalmente não corresponde à expressão de taxa de uma reação de etapa única, que é corroborada pela presença observada de átomos de oxigênio - uma reação intermediária.
Assim, um mecanismo de reação é proposto onde todas as etapas se acumulam para dar a reação geral.
Primeiro, as constantes de taxa indicam que a primeira etapa é a etapa de limitação de taxa. É o mais lento e, portanto, influencia a taxa geral de reação. Uma lei de taxa proposta a partir desta etapa pode ser definida como igual à lei de taxa geral.
Esta lei de taxa proposta, derivada diretamente da concentração molecular do reagente elementar, corresponde à lei de taxa experimental e verifica o mecanismo de reação previsto.
Este texto foi adaptado de <a href="https://openstax.org/books/chemistry-2e/pages/12-6-reaction-mechanisms">Openstax, Chemistry 2e, 12.6: Reaction Mechanisms</a>.

reações em múltiplas etapas

As reações químicas geralmente ocorrem de forma gradual, envolvendo duas ou mais reações distintas ocorrendo em uma sequência. Uma equação balanceada indica as espécies reagentes e os produtos, mas não revela detalhes sobre como a reação ocorre no nível molecular. O mecanismo de reação (ou caminho da reação) fornece detalhes sobre o processo preciso e passo a passo pelo qual uma reação ocorre. Cada uma das etapas de um mecanismo de reação é chamada de reação elementar. Essas reações elementares ocorrem em sequência, conforme representado nas equações das etapas, e se somam para produzir a equação química balanceada que descreve a reação geral. Em um mecanismo de reação de múltiplas etapas, um das etapas elementares progride mais lentamente do que as outras – por vezes significativamente mais lento. Essa etapa mais lenta é chamada de etapa limitante da velocidade (ou etapa determinante da velocidade). Uma reação não pode prosseguir mais rápido do que sua etapa mais lenta e, portanto, a etapa determinante da velocidade limita a velocidade geral da reação.

Ao contrário das equações balanceadas que representam uma reação global, as equações para reações elementares são representações explícitas da mudança química. Uma equação de reação elementar mostra o(s) reagente(s) real(is) submetido(s) à quebra/formação de ligação e o(s) produto(s) formado(s). As leis de velocidade podem ser derivadas diretamente das equações químicas balanceadas para reações elementares. No entanto, este não é o caso da maioria das reações químicas, onde equações balanceadas muitas vezes representam a mudança global no sistema químico resultante de mecanismos de reação em múltiplas etapas. Portanto, a lei de velocidade deve ser determinada a partir de dados experimentais, e o mecanismo de reação deve ser deduzido posteriormente a partir da lei da velocidade.

Por exemplo, considere a reação de NO_2 e CO:

<img alt="Figure1" src="/files/ftp_upload/11699/11699_Equation1.svg" style="text-align: center; height: 22px;">

A lei de velocidade experimental para esta reação em temperaturas acima de 225 °C é:

<img alt="Figure2" src="/files/ftp_upload/11699/11699_Equation2.svg" style="text-align: center; height: 19px;">

 De acordo com a lei de velocidade, a reação é de primeira ordem em relação ao NO_2 e de primeira ordem em relação ao CO. No entanto, em temperaturas abaixo de 225 °C, a reação é descrita por uma lei de velocidade diferente que é de segunda ordem em relação para NO_2:

<img alt="Figure3" src="/files/ftp_upload/11699/11699_Equation3.svg" style="text-align: center; height: 21px;">

 Esta lei de velocidade não é consistente com o mecanismo de etapa única, mas é consistente com o seguinte mecanismo de duas etapas:

<img alt="Figure4" src="/files/ftp_upload/11699/11699_Equation4.svg" style="text-align: center; height: 21px;">

<img alt="Figure5" src="/files/ftp_upload/11699/11699_Equation5.svg" style="text-align: center; height: 21px;">

 A etapa determinante da velocidade (mais lenta) fornece uma lei de velocidade que mostra uma dependência de segunda ordem em relação à concentração de NO_2, e a soma das duas equações elementares fornece a reação global líquida.

Em geral, quando a etapa determinante da velocidade (mais lenta) é a primeira etapa no mecanismo de reação, a lei da velocidade para a reação geral é a mesma que a lei da velocidade para essa etapa. Contudo, quando a etapa determinante da velocidade é precedida por uma etapa elementar envolvendo uma reação rapidamente reversível, a lei da velocidade para a reação global pode ser mais difícil de derivar, muitas vezes devido à presença de intermediários da reação.

Nesses casos, pode ser utilizado o conceito de que uma reação reversível está em equilíbrio quando as velocidades dos processos direto e inverso são iguais.

Reações em Múltiplas Etapas

As reações químicas geralmente ocorrem de forma gradual, envolvendo duas ou mais reações distintas ocorrendo em uma sequência. Uma equação balanceada indica ...

Education

JoVE Core

Organic Chemistry

Química Orgânica

Unit 1

Unidade 1

Thermodynamics and Chemical Kinetics

Termodinâmica e Cinética Química

KEY TERMS AND CONCEPTS

TERMOS-CHAVE E CONCEITOS

reaction mechanisms and rate-determining steps

Chemical reactions can happen in a sequence of steps. A balanced chemical equation shows the reactants and products, but it does not show how the reaction occurs at the molecular level. The reaction mechanism, or reaction path, gives that step-by-step detail.

Each step in a mechanism is an elementary reaction. These elementary reactions happen in order, and together they add up to the balanced equation for the overall reaction. In a multistep mechanism, one step is often much slower than the others. This slowest step is the rate-limiting step, also called the rate-determining step.

The rate-determining step controls how fast the whole reaction can go. A reaction cannot move faster than its slowest step. Unlike an overall balanced equation, an elementary reaction shows the actual reactants that break and form bonds.

For elementary reactions, the rate law can be written directly from the chemical equation. For most reactions, that is not possible because the balanced equation represents the overall change, not each step. In those cases, the rate law must be found from experiments, and the mechanism is then deduced from that rate law.

The reaction between NO2 and CO shows how this works. At temperatures above 225 °C, the experimental rate law is first-order in NO2 and first-order in CO. At temperatures below 225 °C, the rate law is different and is second-order in NO2. That lower-temperature rate law does not fit a single-step mechanism, but it does fit a two-step mechanism.

In that two-step mechanism, the slower step produces the rate law with second-order dependence on NO2. The two elementary equations then combine to give the net overall reaction. In general, when the rate-determining step is the first step, the overall rate law matches that step.

The rate law can be harder to work out when a fast reversible step comes before the slow step. This can happen because intermediates form during the reaction. In those cases, the idea of equilibrium is useful, where the forward and reverse rates are equal.

Reaction Mechanisms and Rate-Determining Steps

reaction-mechanisms-and-rate-determining-steps

chemical reactions

Stoichiometry, Rates, and Equilibrium

Stoichiometry, reaction rates, and equilibrium explain how chemical reactions are measured and predicted. A balanced chemical equation shows the chemical formulas of the reactants and products in a chemical change. It also gives the relative amounts of each substance involved. Reaction stoichiometry helps predict how much reactant is needed to make a desired amount of product. It can also show how much product forms from a given amount of reactant. The amounts shown by a balanced equation are...

enthalpy and heat of reaction

Combustion Heat and Hydrocarbon Stability

Combustion is a burning reaction that releases energy as heat, light, or sound. It happens when a substance reacts with an oxidizing agent, usually molecular oxygen. The heat of combustion is also called the enthalpy of combustion. The energy released when one mole of a substance undergoes complete combustion at constant pressure is the molar heat of combustion. Combustion reactions are exothermic, so they give off energy. For that reason, the sign of ΔH is negative. In 1772, Antoine Lavoisier...

energetics of solution formation

Why Some Solutions Form Spontaneously

Solution formation can happen spontaneously under the right conditions. A spontaneous process is one that occurs without energy from an outside source. During dissolution, solute and solvent particles separate and then attract each other in a new way. The energy change depends on the balance of intermolecular forces, which are the attractions between particles. If the solute-solute and solvent-solvent forces are about the same as the new solute-solvent forces, the solution forms with no energy...

entropy and solvation

Hydrophobic Effects in Solvation

Solvation is the process of surrounding a solute with solvent. It spreads the solute evenly through the solvent. A useful rule is that like dissolves like. A good solvent has molecular features similar to the substance being dissolved. Polar solvents dissolve polar solutes, and apolar solvents dissolve apolar solutes. A polar solvent has a high dielectric constant, with ε greater than or equal to 15. An apolar solvent has a low dielectric constant. The dielectric constant is defined by the...

gibbs free energy and thermodynamic favorability

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Temperature Effects on Gibbs Free Energy

Temperature changes can decide whether a process is spontaneous. This idea applies to phase changes and to some chemical reactions. The key link is Gibbs free energy, which connects free energy change with enthalpy and entropy. The sign of the Gibbs free energy change, or ΔG, depends on the signs of enthalpy change (ΔH) and entropy change (ΔS), and sometimes on the absolute temperature. Because temperature is measured in kelvin, it is always a positive value. That means there are four main...

chemical and solubility equilibria

How Solubility Depends on Free Energy

Solubility depends on free energy changes when a solute dissolves in a solvent. The free energy change for this process is called the free energy of solution, ΔGsolution. When ΔGsolution is less than zero, solution formation is favorable. When it is greater than zero, solution formation is unfavorable. For complete dissolution to happen, the Gibbs energy change must be negative. This means the balance of forces in the mixture must favor solution formation. The amount a solute dissolves in a...

rate law and reaction order

How Reactant Concentration Sets Reaction Rate

Reaction rate depends on reactant concentration, and rate laws show that relationship with a mathematical equation. A rate law, also called a differential rate law or rate equation, links the rate of a chemical reaction to the concentrations of its reactants. For a generic reaction, a A + b B  products, the rate law can be written as rate = k [A]^m [B]^n. Here, [A] and [B] are the molar concentrations of the reactants. The constant k is the rate constant, and it is specific to one reaction at...

effect of temperature change on reaction rate

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Arrhenius Equation in Reaction Speed

The Arrhenius equation connects activation energy, temperature, and the rate constant, k, for many chemical reactions. It helps explain why some reactions move slowly while others happen faster. In this equation, R is the ideal gas constant, with a value of 8.314 J/mol·K. T is the temperature in kelvin, Ea is the activation energy in joules per mole, e is the constant 2.7183, and A is the frequency factor. The frequency factor, A, describes how often reacting molecules collide and how well...

multi-step reactions

Chemical reactions can happen in a sequence of steps. A balanced chemical equation shows the reactants and products, but it does not show how the reaction occurs at the molecular level. The reaction mechanism, or reaction path, gives that step-by-step detail. Each step in a mechanism is an elementary reaction. These elementary reactions happen in order, and together they add up to the balanced equation for the overall reaction. In a multistep mechanism, one step is often much slower than the...

bond dissociation energy and activation energy

bond-dissociation-energy-and-activation-energy

How Bond Strength Shapes Reaction Speed

Bond strength and activation energy help explain why organic reactions happen. Bond energy is the energy needed to break a bond homolytically, which means each atom takes one of the shared electrons. When a bond value is given for one specific bond, it is called bond dissociation energy. When it is given for a bond type across many compounds, it is called average bond energy. Bond dissociation energy usually follows a clear pattern. A single bond is weaker than a double bond, and a double bond...

energy diagrams, transition states, and intermediates

energy-diagrams-transition-states-and-intermediates

Reaction Coordinate Diagrams in Chemical Reactions

Reaction coordinate diagrams show how energy changes during a chemical reaction. These free-energy graphs use the horizontal axis to show reaction progress. Points near the reactants look like the reactants, while points near the products look like the products. The peaks on the diagram represent stable structures with measurable lifetimes. Other points on the curve are unstable and cannot be isolated. The high-energy, unstable peak is called the transition state, or activated complex. At the...

predicting reaction outcomes

How Temperature Changes Reaction Rate

Reaction rate and reaction pathway are key ideas in chemical kinetics. Thermodynamics, by contrast, focuses on the state of a system. It describes the properties, behavior, and components of reactants and products. It does not describe the path of the process or the speed of the reaction. Kinetics gives information on the atomic or molecular level, while thermodynamics focuses on the energetics of the reactants and products. Thermodynamics can show what may happen in a reaction, but it does...

key terms and concepts

Learn how reaction mechanisms work, why the slowest step limits reaction rate, and how rate laws help identify multistep reactions in chemistry.

Reaction Mechanisms and Rate-Determining Steps | JoVE K12

organic chemistry

JoVE Core - Química Orgânica explica conceitos básicos de estereoquímica, reações e mecanismos usando vídeos de animação concisos e fáceis de entender. Além disso, os vídeos de Cientistas em ação demonstram a aplicação de conceitos relacionados em experimentos de pesquisa clássicos e originais realizados nos laboratórios atuais em todo o mundo.

Next Generation Science Standards

Physical Science

Matter and Its Interactions

HS-PS1-2

HS-PS1-7

south-carolina-college-and-career-ready-science-standards

South Carolina College and Career Ready Science Standards

C-PS1-4

C-PS1-5

C-PS1-6

The Periodic Table

As early chemists discovered more elements, they realized that various elements could be grouped by their similar chemical behaviors. One such grouping ...

Periodic Classification of the Elements

The periodic table arranges atoms based on increasing atomic number so that elements with the same chemical properties recur periodically. When their ...

the-periodic-table-and-organismal-elements

The Periodic Table And Organismal Elements

Atomic Structure

The Greek philosopher Democritus proposed that everything on Earth is made up of tiny particles called atomos, Greek for &#34;indivisible,&#34; from which ...

Electron Configurations

Electron configurations and orbital diagrams can be determined by applying the Aufbau principle (each added electron occupies the subshell of lowest ...

Electronic Structure of Atoms


An atom comprises protons and neutrons, which are contained inside the dense, central&#160;core called the nucleus, with electrons present around the ...

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Electron Configuration of Multielectron Atoms

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Atomic Radii and Effective Nuclear Charge

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The Aufbau Principle and Hund's Rule

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Sources and Properties of Electric Charge

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Electric Fields

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Intermolecular Forces

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Van der Waals Interactions

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Chemical Bonds


Atoms participate in a chemical bond formation&#160;to acquire a completed valence-shell electron configuration similar to that of the noble gas nearest ...

Electron Behavior

Electrons are negatively charged subatomic particles attracted to and orbit around the positively-charged nucleus of an atom. They reside in spaces ...

Subatomic Particles

Dalton was only partially correct about the particles that make up matter. All matter is composed of atoms, and atoms are composed of three smaller ...

Ions and Ionic Charges

In ordinary chemical reactions, the nucleus &mdash; which contains the protons and neutrons of each atom and thus identifies the element &mdash; remains ...

Use the periodic table as a model to predict the relative properties of elements based on the patterns of electrons in the outermost energy level and the composition of the nucleus of atoms.  Clarification Statement: Chemistry: Examples of properties that could be predicted from patterns could include reactivity of metals, types of bonds formed, numbers of bonds formed, atomic radius, atomic mass, or reactions with oxygen. Emphasis is on main group elements and qualitative understanding of the relative trends of ionization energy and electronegativity.

HS-PS1-1

Properties of Transition Metals

Transition metals are defined as those elements that have partially filled d orbitals. As shown in Figure 1, the d-block elements in groups 3&#8211;12 are ...

The Atomic Theory of Matter

The earliest recorded discussion of the basic structure of matter comes from ancient Greek philosophers. Leucippus and Democritus argued that all matter ...

Chemical Reactions

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Chemical Equations

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The Collision Theory
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Stoichiometry, Product Yield, and Limiting Reactants

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Physical and Chemical Properties of Matter

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Physical Properties of Matter

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Dynamic Equilibrium

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Construct and revise an explanation for the outcome of a simple chemical reaction based on the outermost electron states of atoms, trends in the periodic table, and knowledge of the patterns of chemical properties.  Clarification Statement: Chemistry: Examples of chemical reactions could include the reaction of sodium and chlorine, carbon and oxygen, or carbon and hydrogen. Reaction classification aids in the prediction of products (e.g. synthesis, decomposition, single displacement, double displacement, and acid-base).

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Comparison Between Electrical And Gravitational Forces

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Intermolecular Forces and Physical Properties



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Electric Field of Two Equal and Opposite Charges

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Ionic Bonding and Electron Transfer

Ions are atoms or molecules bearing an electrical charge. A cation (a positive ion) forms when a neutral atom loses one or more electrons from its valence ...

Electric Dipoles and Dipole Moment

Consider two charges of equal magnitude but opposite signs. If they cannot be separated by an external electric field, the system is called a permanent ...

Plan and conduct an investigation to gather evidence to compare the structure of substances at the macroscale to infer the strength of electrical forces between particles.  Clarification Statement: Emphasis is on understanding the strengths of forces between particles, not on naming specific intermolecular forces (such as dipole-dipole). Examples of particles could include ions, atoms, molecules, and network solids (such as graphite). Examples of macro-properties of substances could include the melting point and boiling point, vapor pressure, and surface tension.

HS-PS1-3

Bond Dissociation Energy and Activation Energy

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Bond Energies and Bond Lengths

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Coupled Reactions

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Energy Diagrams, Transition States, and Intermediates

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What is Metabolism?

Overview

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Types of Chemical Reactions: Anabolic and Catabolic

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Non-equilibrium in the Cell

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Activation Energy

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Energy Transfer in Chemical Reactions

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Factors Influencing the Rate of Chemical Reactions

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Predicting Reaction Outcomes

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States of Matter and Phase Changes

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Reaction Mechanisms

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Temperature Dependence

Chemical Kinetics 
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Develop a model to illustrate that the release or absorption of energy from a chemical reaction system depends upon the changes in total bond energy.  Clarification Statement: Emphasis is on the idea that a chemical reaction is a system that affects the energy change.  Examples of models could include molecular-level drawings and diagrams of reactions, graphs showing the relative energies of reactants and products, and representations showing energy is conserved.

HS-PS1-4

Reaction Mechanisms and Rate-Determining Steps

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