On a metal surface

The most common technique for estimating thermal stability is called the Jet Fuel Thermal Oxidation Test (JFTOT). It shows the tendency of the fuel to form deposits on a metallic surface brought to high temperature. The sample passes under a pressure of 34.5 bar through a heated aluminum tube (260°C for Jet Al). After two and one-half hours, the pressure drop across a 17-micron filter placed at the outlet of the heater is measured (ASTM D 3241). 

If the desorption rate is second-order, as is often the case for hydrogen on a metal surface, so that appears in Eq. XVIII-1, an equation analogous to Eq. XVIII-3 can be derived by the Redhead procedure. Derive this equation. In a particular case, H2 on Cu3Pt(III) surface, A was taken to be 1 x 10 cm /atom, the maximum desorption rate was at 225 K, 6 at the maximum was 0.5. Monolayer coverage was 4.2 x 10 atoms/cm, and = 5.5 K/sec. Calculate the desorption enthalpy (from Ref. 110). 

Hydrogen atoms chemisorbed on a metal surface may be bonded to just one metal atom or may be bonded to two atoms in a symmetrical bridge. In each case, there are three normal modes. Sketch what these are, and indicate any degeneracies (assume the metal atoms to be infinitely heavy). 

Crommie M F, Lutz C P and Eigler D M 1993 Confinement of electrons to quantum corrals on a metal surface Science 262 218... 

Corrosion protection of metals can take many fonns, one of which is passivation. As mentioned above, passivation is the fonnation of a thin protective film (most commonly oxide or hydrated oxide) on a metallic surface. Certain metals that are prone to passivation will fonn a thin oxide film that displaces the electrode potential of the metal by +0.5-2.0 V. The film severely hinders the difflision rate of metal ions from the electrode to tire solid-gas or solid-liquid interface, thus providing corrosion resistance. This decreased corrosion rate is best illustrated by anodic polarization curves, which are constructed by measuring the net current from an electrode into solution (the corrosion current) under an applied voltage. For passivable metals, the current will increase steadily with increasing voltage in the so-called active region until the passivating film fonns, at which point the current will rapidly decrease. This behaviour is characteristic of metals that are susceptible to passivation. 

Figure A3.10.23 Schematic diagram of molecular CO chemisorption on a metal surface. The model is based on a donor-acceptor scheme where the CO 5 a FIOMO donates charge to surface unoccupied states and the surface back-donates charge to the CO 2 71 LUMO [58].

However, many adsorbates caimot reach a coverage of 1 ML as defined in this way this occurs most clearly when the adsorbate is too large to fit in one unit cell of the surface. For example, benzene molecules nonnally lie flat on a metal surface, but the size of the benzene molecule is much larger than typical unit cell areas on many metal surfaces. Thus, such an adsorbate will saturate the surface at a lower coverage than 1 ML deposition beyond this coverage can only be achieved by starting the growdi of a second layer on top of the first layer. 

NakatsujI H, Nakal H and Fukunishi Y 1991 Dipped adcluster model for chemisorptions and catalytic reactions on a metal surface Image force correction and applications to Pd-02 adclusters J. Chem. Phys. 95 640-7 NakatsujI H and Nakal H 1992 Dipped adcluster model study for the end-on chemisorption of O2 on an Ag surface Can. J. Chem. 70 404-8... 

Figure C2.8.5. Growth of an oxide film on a metal surface, (a) In tire absence of an externally applied potential ...

If photons of light of a suitable wavelength (usually ultraviolet or x-rays) impinge on a metal surface, electrons are emitted. This effect is photoelectric (or photovoltaic) and can be used to start a flow of electrons in a discharge tube. 

Similarly, adsorption of ions (n+) onto a metal surface leads to a heat of adsorption of Q,. Generally, Q is about 2-3 eV and is greater than Q, which itself is about 1 eV. The difference between Q, and is the energy required to ionize neutrals (n ) on a metal surface so as to give ions (n+) or vice versa. This difference, Q - Q, can be equal to, greater than, or less than the difference, I - ( ), between the ionization energy (1) of the neutral and the ease with which a metal can donate or accept an electron (the work function, ( )). Where Q, - Q, > I - ( ), the adsorbed... 

MOLE, however, is more sensitive than ETIR (<1 samples compared to about 100 p.m ). With surface-enhanced Raman spectroscopy the Raman signal is enhanced by several orders of magnitude. This requires that the sample be absorbed on a metal surface (eg, Ag, Cu, or Au). It also yields sophisticated characterization data for the polytypes of siUcon carbide, graphite, etc. 

CO Oxidation Catalyzed by Palladium. One of the best understood catalytic reactions occurring on a metal surface is the oxidation of carbon monoxide on palladium ... 

Cavitation Formation of transient voids or vacuum bubbles in a liquid stream passing over a surface is called cavitation. This is often encountered arouna propellers, rudders, and struts and in pumps. When these bubbles collapse on a metal surface, there is a severe impact or explosive effec t that can cause considerable mechanical damage, and corrosion can be greatly accelerated because of the destruction of protective films. Redesign or a more resistant metal is generally required to avoid this problem. 

Conventionally RAIRS has been used for both qualitative and quantitative characterization of adsorbed molecules or films on mirror-like (metallic) substrates [4.265]. In the last decade the applicability of RAIRS to the quantitative analysis of adsorbates on non-metallic surfaces (e.g. semiconductors, glasses [4.267], and water [4.273]) has also been proven. The classical three-phase model for a thin isotropic adsorbate layer on a metallic surface was developed by Greenler [4.265, 4.272]. Calculations for the model have been extended to include description of anisotropic layers on dielectric substrates [4.274-4.276]. 

Deposit attack occurs when there is nonuniform deposition of a film on a metal surface. The most common form appears as unequal scale deposits in an aqueous environment. Unequal film provides for concentration cells, which degrade the metal by galvanic means. 

Deposit Attack—to localized corrosion under, and resulting from, a deposit on a metal surface. 

Scaling—the formation of thick corrosion products as layers on a metal surface in piping systems it is usually the deposition of water-insoluble constituents on a metal surface. 

Most black pigments are made of carbon black formed by depositing carbon from a smoky flame of natural gas on a metal surface. Lampblack is made similarly by burning oik Bone blacks are made from charred bones. Graphite occurs naturally or can be prepared from coal in electric furnaces. Mineral blacks come from shale, peat, and coal dust. Iron oxide blacks are found in nature or prepared. Blue lead sulfate is a pigment for priming. Of these, carbon black is su[XTinr. 

Catalytic hydrogenation of alkynes on a metal surface provides cis alkenes (see Chapter 7, Problem 13), while treatment with sodium in liquid ammonia nearly always leads to trans alkenes, e.g., hydrogenation of 2-butyne. 

Conditions necessary for the onset of corrosion are quite often provided by heterogeneities. These heterogeneities may very well exist within the metal or alloy or may be imposed by external factors. These heterogeneities can give rise to variations in potential on a metal surface immersed in an electrolytic fluid. The galvanic cell thus formed gives rise to flow of current that accompanies corrosion [188]. 

Sulfur compounds, whether organic or inorganic in nature, cause sulfidation in susceptible materials. The sulfide film, which forms on the surface of much con-stmction materials at low temperatures, becomes friable and melts at higher temperatures. The presence of molten sulfides (especially nickel sulfide) on a metal surface promotes the rapid conversion to metal sulfides at temperatures where these sulfides are thermodynamically stable. High-alloy materials such as 25% Cr, 20% Ni alloys are widely used, but these represent a compromise between sulfidation resistance and mechanical properties. Aluminum and similar diffusion coatings can be of use. 

Impingement attack (sometimes termed erosion corrosion) is a result of the combined effect of flow and corrosion on a metal surface and it occurs when metal is removed from the surface under conditions where passivation is insufficiently rapid. It is a function of flow, corrosion and passivation. 

This limited survey has indicated the wide range of chemical compounds, particularly oxides, which may be formed on a metal surface as a result of a corrosion process. The nature of such films and scales needs to be carefully characterised. Fortunately, a wide spectrum of experimental techniques is now available to provide such valuable information, and others are under development. A convenient summary is provided in Table 1.6. 

The above considerations show that the rate of a corrosion reaction is dependent on both the thermodynamic parameter and the kinetic parameters rjj and rjj. It is also apparent that (q) the potential actually measured when corrosion reaction occurs on a metal surface is mixed, compromise or corrosion potential whose magnitude depends on E, and on the Ej, -I and Ej, -I relationships, and (b) direct measurement of 7 is not possible when the electrodes are inseparable. 

Crevices or deposits on a metal surface or any other geometrical configuration that results in differences in the concentration of the cathodic reactant... 

Although the Langelier index is probably the most frequently quoted measure of a water s corrosivity, it is at best a not very reliable guide. All that the index can do, and all that its author claimed for it is to provide an indication of a water s thermodynamic tendency to precipitate calcium carbonate. It cannot indicate if sufficient material will be deposited to completely cover all exposed metal surfaces consequently a very soft water can have a strongly positive index but still be corrosive. Similarly the index cannot take into account if the precipitate will be in the appropriate physical form, i.e. a semi-amorphous egg-shell like deposit that spreads uniformly over all the exposed surfaces rather than forming isolated crystals at a limited number of nucleation sites. The egg-shell type of deposit has been shown to be associated with the presence of organic material which affects the growth mechanism of the calcium carbonate crystals . Where a substantial and stable deposit is produced on a metal surface, this is an effective anticorrosion barrier and forms the basis of a chemical treatment to protect water pipes . However, the conditions required for such a process are not likely to arise with any natural waters. 

Chemical Conversion Coating a protective or decorative coating which is produced deliberately on a metal surface by a chemical environment. 

Corrosion inhibition, by mechanical deposition of crystalline or amorphous films on a metal surface. 

Chemical that reduces the tendency of iron to oxidize (rust) to ferrous ion, such as chromate which suppresses that part of the electrolytic corrosion process occurring at the anodic sites on a metal surface. 

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