Surface chemistry

Surface chemistry can be roughly defined as the study of chemical reactions at interfaces. It is closely related to surface engineering, which aims at modifying the chemical composition of a surface by incorporation of selected elements or functional groups that produce various desired effects or improvements in the properties of the surface or interface. The adhesion of gas or liquid molecules to the surface is known as adsorption. This can be due to either chemisorptions or by physisorption. These too are included in surface chemistry.

Absorption
Absorption, in chemistry, is a physical or chemical phenomenon or a process in which atoms, molecules, or ions enter some bulk phase - gas, liquid, or solid material. This is a different process from adsorption, since molecules undergoing absorption are taken up by the volume, not by the surface (as in the case for adsorption).

Adsorption
Adsorption is the adhesion of atoms, ions, `bimolecular or molecules of gas, liquid, or dissolved solids to a surface. This process creates a film of the adsorb ate (the molecules or

atoms being accumulated) on the surface of the adsorbent. It differs from absorption, in which a fluid permeates or is dissolved by a liquid or solid. The term sorption encompasses both processes, while desorption is the reverse of adsorption. It is a surface phenomenon. The adsorption process is generally classified as physisorption (characteristic of weak van deer Waals forces) or chemisorptions (characteristic of covalent bonding). It may also occur due to electrostatic attraction. Adsorption is present in many natural physical, biological, and chemical systems, and is widely used in industrial applications such as activated charcoal, capturing and using waste heat to provide cold water for air conditioning and other process requirements (adsorption chillers), synthetic resins, increase storage capacity of carbide-derived carbons for tunable nonporous carbon, and water purification.

Adsorbents
Characteristics and general requirements

Adsorbents are used usually in the form of spherical pellets, rods, moldings, or monoliths with hydrodynamic diameters between 0.5 and 10 mm. They must have high abrasion resistance, high thermal stability and small pore diameters, which results in higher exposed surface area and hence high surface capacity for adsorption. The adsorbents must also have a distinct pore structure which enables fast transport of the gaseous vapors. Most industrial adsorbents fall into one of three classes: Oxygen-containing compounds Are typically hydrophilic and polar, including materials such as silica gel and zealots. Carbon-based compounds Are typically hydrophobic and non-polar, including materials such as activated carbon and graphite. Polymer-based compounds - Are polar or non-polar functional groups in a porous polymer matrix.

Silica gel
Silica gel is a chemically inert, nontoxic, polar and dimensionally stable (< 400 C or 750 F) amorphous form of SiO2. It is prepared by the reaction between sodium silicate and acetic acid, which is followed by a series of after-treatment processes such as aging, pickling, etc. These after treatment methods results in various pore size distributions. Silica is used for drying of process air (e.g. oxygen, natural gas) and adsorption of heavy (polar) hydrocarbons from natural gas.

Zealots
Zealots are natural or synthetic crystalline aluminosilicates which have a repeating pore network and release water at high temperature. Zealots are polar in nature. Zealots are applied in drying of process air, CO2 removal from natural gas, CO removal from reforming gas, air separation, catalytic cracking, and catalytic synthesis and reforming.

Activated carbon
Activated carbon is a highly porous, amorphous solid consisting of microcrystallines with a graphite lattice, usually prepared in small pellets or a powder. It is non-polar and cheap. One of its main drawbacks is that it is reacts with oxygen at moderate temperatures (over 300 C).

Activated carbon can be manufactured from carbonaceous material, including coal (bituminous, sub bituminous, and lignite), peat, wood, or nutshells (e.g., coconut). Activated carbon is used for adsorption of organic substances and non-polar adsorbents and it is also usually used for waste gas (and waste water) treatment. It is the most widely used adsorbent since most of its chemical (e.g. surface groups) and physical properties (e.g. pore size distribution and surface area) can be tuned according to what is needed. Its usefulness also derives from its large microspore (and sometimes mesopore) volume and the resulting high surface area.

Chemisorptions
Chemisorptions is a sub-class of adsorption, driven by a chemical reaction occurring at the exposed surface. A new chemical species is generated at the adsorbent surface (e.g. corrosion, metallic oxidation). The strong interaction between the adsorb ate and the substrate surface creates new types of electronic bonds - ionic or covalent, depending on the reactive chemical species involved.

It is characterized by:

An activation energy for the chemical reaction that takes place only in a monolayer A high enthalpy change/ temperature gain, indicating an exothermic chemical reaction. Due to specificity, the nature of chemisorptions can greatly differ from system to system, depending on the chemical identity and the surface structure.

Uses
The main way in which most chemists utilize the effect of chemisorptions is in catalyzed reactions. The process of chemisorptions is actually pivotal to the role of heterogeneous catalysis where the catalyst is in a solid phaseparticularly transition metal catalysts.

Examples
Self-assembled monolayers (SAMs) are often formed by chemisorbing thrills (RS-H) onto gold surfaces forming Au-SR bonds. O2 on carbon at high temperatures.

Research is ongoing on the adsorption of hydrogen onto carbon annotates with the aim of producing a fuel cell that can eventually replace our dependence on fossil fuels.

Physisorption
Physisorption, also called physical adsorption, is a process in which the electronic structure of the atom or molecule is barely perturbed upon adsorption. The weak bonding of physisorption is due to the induced dipole moment of a no polar adsorb ate interacting with its own image charge in the polarizable solid. The fundamental interacting force of physisorption is caused by van der Waals force. Even though the interaction energy is very weak, physisorption plays an important role in nature. For instance, the van der Waals attraction between surfaces and foot-hairs of geckos provides the remarkable ability to climb up vertical walls. In the point of view of molecular physics, the van der Waals attractive force originates from the charge fluctuations between two correlated bonding molecules or atoms, in other words, the mutually induced dipole moments. In comparison with chemisorptions, in which the electronic structure of bonding atoms or molecules is changed and covalent or ionic bonds form, physisorption, generally speaking, can only be observed in the environment of low temperature and the absence of the relatively strong chemisorptions.

Comparison with chemisorptions

Physisorption is a general phenomenon and occurs in any solid/fluid or solid/gas system. Chemisorptions is characterized by chemical specificity.

In physiorption, perturbation of the electronic states of adsorbent and adsorb ate is minimal. For chemisorptions, changes in the electronic states may be detectable by suitable physical means. Typical binding energy of physisorption is about 10100 me. Chemisorptions usually forms bonding with energy of 110 eve. The elementary step in physisorption from a gas phase does not involve an activation energy. Chemisorptions often involves an activation energy. For physisorption, under appropriate conditions, gas phase molecules can form multilayer adsorption. In chemisorptions, molecules are adsorbed on the surface by valence bonds and only form monolayer adsorption.

Catalysis
Catalysis is the change in rate of a chemical reaction due to the participation of a substance called a catalyst. Unlike other reagents that participate in the chemical reaction, a catalyst is not consumed by the reaction itself. A catalyst may participate in multiple chemical transformations. Catalysts that speed the reaction are called positive catalysts. Substances that slow a catalyst's effect in a chemical reaction are called inhibitors. Substances that increase the activity of catalysts are called promoters, and substances that deactivate catalysts are called catalytic poisons.

Catalytic reactions have a lower rate-limiting free energy of activation than the corresponding unanalyzed reaction, resulting in higher reaction rate at the same temperature. Catalysts may affect the reaction environment favorably, or bind to the reagents to polarize bonds. Kinetically, catalytic reactions are typical chemical reactions; i.e. the reaction rate depends on the frequency of contact of the reactants in the rate-determining step. Usually, the catalyst participates in this slowest step, and rates are limited by amount of catalyst and its "activity". In heterogeneous catalysis, the diffusion of reagents to the surface and diffusion of products from the surface can be rate determining. Analogous events associated with substrate binding and product dissociation apply to homogeneous catalysts. Although catalysts are not consumed by the reaction itself, they may be inhibited, deactivated, or destroyed by secondary processes.

Catalysis and reaction energetic

Generic potential energy diagram showing the effect of a catalyst in a hypothetical exothermic chemical reaction X + Y to give Z. The presence of the catalyst opens a different reaction pathway (shown in red) with a lower activation energy. The final result and the overall thermodynamics are the same. Catalysts work by providing an (alternative) mechanism involving a different transition state and lower activation energy. Consequently, more molecular collisions have the energy needed to reach the transition state. Hence, catalysts can enable reactions that would otherwise be blocked or slowed by a kinetic barrier. The catalyst may increase reaction rate or selectivity, or enable the reaction at lower temperatures. In the catalyzed elementary reaction, catalysts do not change the extent of a reaction: they have no effect on the chemical equilibrium of a reaction because the rate of both the forward and the reverse reaction are both affected . Production of energy is a necessary result since reactions are spontaneous if and only if Gibbs free energy is produced, and if there is no energy barrier, there is no need for a catalyst. Then, removing the catalyst would also result in reaction, producing energy; i.e. the addition and its reverse process, removal, would both produce energy.

Types of catalysis
Catalysts can be either heterogeneous or homogeneous, depending on whether a catalyst exists in the same phase as the substrate. Biocatalysts (enzymes) are often seen as a separate group.

Heterogeneous catalysts

The micro porous molecular structure of the elite ZSM-5 is exploited in catalysts used in refineries

Zealots are extruded as pellets for easy handling in catalytic reactors. Heterogeneous catalysts act in a different phase than the reactants. Most heterogeneous catalysts are solids that act on substrates in a liquid or gaseous reaction mixture.The total surface area of solid has an important effect on the reaction rate. The smaller the catalyst particle size, the larger the surface area for a given mass of particles. For example, in the Haber process, finely divided iron serves as a catalyst for the synthesis of ammonia from nitrogen and hydrogen. The reacting gases adsorb onto "active sites" on the iron particles. Once adsorbed, the bonds within the reacting molecules are weakened, and new bonds between the resulting fragments form in part due to their close proximity. In this way the particularly strong triple bond in nitrogen is weakened and the hydrogen and nitrogen atoms combine faster than would be the case in the gas phase, so the rate of reaction increases. Another place where a heterogeneous catalyst is applied is in the contact process (oxidation of sulfur dioxide on vanadium(V) oxide for the production of sulfuric acid).

Homogeneous catalysts

Homogeneous catalysts function in the same phase as the reactants, but the mechanistic principles involved in heterogeneous catalysis are generally applicable. Typically homogeneous catalysts are dissolved in a solvent with the substrates. One example of homogeneous catalysis involves the influence of H+ on the etherification of esters, e.g. methyl acetate from acetic acid and methanol. For inorganic chemists, homogeneous catalysis is often synonymous with organ metallic catalysts.

A palladium complex

used as Homogeneous

catalyst

Significance of catalysis

left: Partially caramelized cube sugar, right: burning cube sugar with ash as catalyst

Estimates are that 90% of all commercially produced chemical products involve catalysts at some stage in the process of their manufacture. In 2005, catalytic processes generated about $900 billion in products worldwide. Catalysis is so pervasive that subareas are not readily classified.

Energy processing
Petroleum refining makes intensive use of catalysis for alkylation, catalytic cracking (breaking long-chain hydrocarbons into smaller pieces), naphtha reforming and steam reforming (conversion of hydrocarbons into synthesis gas). With regard to synthetic fuels, an old but still important process is the Fischer-Tropic synthesis of hydrocarbons from synthesis gas, which itself is processed via water-gas shift reactions, catalyzed by iron. Biodiesel and related befouls require processing via both inorganic and biocatalysts. Fuel cells rely on catalysts for both the anodic and catholic reactions.

Bulk chemicals
Some of the largest-scale chemicals are produced via catalytic oxidation, often using oxygen. Examples include nitric acid (from ammonia), sulfuric acid (from sulfur dioxide to sulfur trioxide by the chamber process), terephthalic acid from p-xylem, and acrylonitrile from propane and ammonia. Many other chemical products are generated by large-scale reduction, often via hydrogenation. The largest-scale example is ammonia, which is prepared via the Haber process from nitrogen. Methanol is prepared from carbon monoxide.Most carbonization processes require metal catalysts, examples include the Monsanto acetic acid process and hydroformylation.

Fine chemicals
Many fine chemicals are prepared via catalysis; methods include those of heavy industry as well as more specialized processes that would be prohibitively expensive on a large scale. Examples include olefin metathesis using Grubbs' catalyst, the Heck reaction, and Frieda-Crafts reactions.

Food processing
One of the most obvious applications of catalysis is the hydrogenation (reaction with hydrogen gas) of fats using nickel catalyst to produce margarine. Many other foodstuffs are prepared via biocatalysts.

In the environment
Catalysis impacts the environment by increasing the efficiency of industrial processes, but catalysis also plays a direct role in the environment. A notable example is the catalytic role of

chlorine free radicals in the breakdown of ozone. These radicals are formed by the action of ultraviolet radiation on chlorofluorocarbons (CFCs). Cal + O3 Clod + O2 Clod + O Cal + O2

Inhibitors, poisons and promoters

Substances that reduce the action of catalysts are called catalyst inhibitors if reversible, and catalyst poisons if irreversible. Promoters are substances that increase the catalytic activity, even though they are not catalysts by themselves. Inhibitors are sometimes referred to as "negative catalysts" since they decrease the reaction rate. However the term inhibitor is preferred since they do not work by introducing a reaction path with higher activation energy; this would not reduce the rate since the reaction would continue to occur by the non-catalyzed path. Instead they act either by inactivating catalysts, or by removing reaction intermediates such as free radicals. The inhibitor may modify selectivity in addition to rate. For instance, in the reduction of ethane to ethane, the catalyst is palladium (Pd) partly "poisoned" with lead(II) acetate (Pb (CH3COO)2). Without the deactivation of the catalyst, the ethane produced will be further reduced to ethane. The inhibitor can produce this effect by e.g. selectively poisoning only certain types of active sites. Another mechanism is the modification of surface geometry. For instance, in hydrogenation operations, large planes of metal surface function as sites of hydrogenolysis catalysis while sites catalyzing hydrogenation of unsaturated are smaller. Thus, a poison that covers surface randomly will tend to reduce the number of uncontaminated large planes but leave proportionally more smaller sites free, thus changing the hydrogenation vs. hydrogenolysis selectivity. Many other mechanisms are also possible.

Promoters can cover up surface to prevent production of a mat of coke, or even actively remove such material (e.g. rhenium on platinum in plat forming). They can aid the dispersion of the catalytic material or bind to reagents.

Enzyme Catalysis
Enzyme catalysis is the catalysis of chemical reactions by specialized proteins known as enzymes. Catalysis of biochemical reactions in the cell is vital due to the very low reaction rates of the unanalyzed reactions. The mechanism of enzyme catalysis is similar in principle to other types of chemical catalysis. By providing an alternative reaction route and by stabilizing intermediates the enzyme reduces the energy required to reach the highest energy transition state of the reaction. The reduction of activation energy (Ea) increases the number of reactant molecules with enough energy to reach the activation energy and form the product.

Stabilization of the transition state by an enzyme.

Colloid
A colloid is a substance microscopically dispersed evenly throughout another substance. A colloidal system consists of two separate phases: a dispersed phase (or internal phase) and a continuous phase (or dispersion medium). A colloidal system may be solid, liquid, or gaseous. Many familiar substances are colloids, as shown in the chart . In addition to these naturally occurring colloids, modern chemical process industries utilize high shear mixing technology to create novel colloids. The dispersed-phase particles have a diameter of between approximately 1 and 1000 nanometers. Such particles are normally invisible in an optical microscope, though their presence can be confirmed with the use of an ultra microscope or an electron microscope. Homogeneous mixtures with a dispersed phase in this size range may be called colloidal aerosols, colloidal emulsions, colloidal foams, colloidal dispersions, or hydrosols. The dispersed-phase particles or droplets are affected largely by the surface chemistry present in the colloid. Some colloids are translucent because of the Tyndall effect, which is the scattering of light by particles in the colloid. Other colloids may be opaque or have a slight color. Colloidal solutions (also called colloidal suspensions) are the subject of interface and colloid science. This field of study was introduced in 1861 by Scottish scientist Thomas Graham.

Classification

Because the size of the dispersed phase may be difficult to measure, and because colloids have the appearance of solutions, colloids are sometimes identified and characterized by their physic-chemical and transport properties. Colloids can be classified as follows: Medium / Phases Gas Continuous medium Dispersed phase Gas Liquid Solid NONE Liquid aerosol Solid aerosol (All gases are mutually Examples: fog, mist, hair Examples: smoke, cloud, miscible) sprays air particulates Emulsion Sol Examples: milk, Examples: pigmented ink, mayonnaise, hand cream blood Gel Solid sol Examples: agar, gelatin, Example: cranberry glass jelly, opal

Foam Liquid Example: whipped cream, Shaving cream Solid Solid foam Examples: aero gel, Styrofoam, pumice

In some cases, a colloid can be considered as a homogeneous mixture. This is because the distinction between "dissolved" and "particulate" matter can be sometimes a matter of approach, which affects whether or not it is homogeneous or heterogeneous.

Preparation of colloids
There are two principal ways of preparation of colloids: Dispersion of large particles to the colloidal dimensions; Condensation of molecules dissolved in a true solution into larger colloidal particles.

Stabilization of a colloidal dispersion (peptization)

The stability of a colloidal system is the capability of the system to remain as it. Stability is hindered by aggregation and by sedimentation phenomena, that determine phase separation.

Examples of a stable and of an unstable colloidal dispersion. Aggregation is due to the sum of the interaction forces between particles. If attractive forces (such as van deer Waals forces) prevail over the repulsive ones (such as the electrostatic ones) particles aggregate in clusters. Electrostatic stabilization and satiric stabilization are the two main mechanisms for stabilization against aggregation.

Electrostatic stabilization is based on the mutual repulsion of like electrical charges. In general, different phases have different charge affinities, so that a electrical double layer forms at any interface. STERIS stabilization consists in covering the particles in polymers which prevents the particle to get close in the range of attractive forces.

Destabilizing a colloidal dispersion (flocculation)

Unstable colloidal dispersions form flocks as the particles aggregate due to antiparticle attractions. In this way photonic glasses can be grown. This can be accomplished by a number of different methods: Removal of the electrostatic barrier that prevents aggregation of the particles. This can be accomplished by the addition of salt to a suspension or changing the pH of a suspension to effectively neutralize or "screen" the surface charge of the particles in suspension. This removes the repulsive forces that keep colloidal particles separate and allows for coagulation due to van deer Waals forces. Addition of non-adsorbed polymers called dilatants that cause aggregation due to entropic effects. Physical deformation of the particle (e.g., stretching) may increase the van deer Waals forces more than stabilization forces (such as electrostatic), resulting coagulation of colloids at certain orientations.

Colloids in the environment

Colloidal particles can also serve as transport vector of diverse contaminants in the surface water (sea water, lakes, rivers, fresh water bodies) and in underground water circulating in fissured rocks (limestone, sandstone, granite, ...). Radionuclides and heavy metals easily sorbs onto colloids suspended in water. Various types of colloids are recognized: inorganic colloids (clay particles, silicates, iron oxy-hydroxides, ...), organic colloids (humic and folic substances). Colloids have been suspected for the long-range transport of plutonium on the Nevada Nuclear Test Site. They have been the subject of detailed studies for many years.