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April 21, 2006

Bulk property

Filed under: Chemistry Terms — @ 8:55 am

Bulk property

In chemistry, materials science, and other scientific disciplines, a bulk property of a substance is one that is independent of the amount of that substance being measured.

For instance, the mass of a substance is not a bulk property, because it depends on the amount of that substance being measured; one cubic meter of lead weighs a million times as much as a cubic centimeter of lead. However, both have the same density; thus, density is a bulk property.

Other examples of bulk properties include refractive index, concentration, half-life, elastic modulus, and tensile strength.

The concept is similar to that of per capita measurements in economics.

Catenation

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Catenation

Catenation is the ability of some elements to form chains of identical atoms. Carbon is the premier element in this respect, but some other elements (for instance, sulfur, silicon, and germanium) possess the property to a lower degree.

Carbon can form covalent bonds with two other carbon atoms and thus can form chains and rings. Aliphatic and aromatic hydrocarbons are examples of catenation. The propensity for catenation is high in carbon because the bond energy of the carbon-carbon bond is high in comparision to the energy of bonds of carbon with other elements.

Other elements, including some Chalcogens such as Sulfur and Oxygen, can also form chain structures. In the case of oxygen, only two-atom chain can be formed.Peroxide is an example. However, for sulfur, 8-atom (or even more than 8) cation is fairly common.

Caustic (substance)

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Caustic (substance)

A caustic substance, in chemistry, is one that causes corrosion, the deterioration of a material. Caustic literally means burning. A caustic substance can be acidic or basic, and concentrated solutions of acids and bases are common corrosive substances. Sodium Hydroxide, also known as caustic soda, is one example. Caustic substances are harmful to living tissue and structures, but they have beneficial uses. For example, drain cleaners often use caustic substances such as NaOH to clear clogged drains.

Chartered Chemist

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Chartered Chemist

Chartered Chemist (CChem) is a chartered status awarded by the Royal Society of Chemistry (RSC) in the United Kingdom and by the Royal Australian Chemical Institute (RACI) in Australia.

In the United Kingdom CChem candidates must meeting the following requirements:

  • Be a Member or a Fellow of the RSC;
  • Hold a degree accredited by the RSC (or equivalent);
  • Show that the chemical knowledge and skills acquired from their education and training are essential for fulfilling the needs of their job;
  • Demonstrate development of twelve Professional Attributes.

In Australia the requirements are broadly the same as above.

Reference

Chemical accidents

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Chemical accidents

Chemical accidents are unanticipated releases, explosions, fires and other harmful incidents involving toxic and hazardous materials. While chemical accidents may occur whenever toxic materials are stored, transported or used, the most severe accidents tend to involve major chemical manufacturing and storage facilities. Significant events include the Bhopal Disaster of 1984, which released a highly toxic gas at a Union Carbide pesticides facility and killed more than 2,000 people.

Efforts to prevent accidents range from improved safety systems to fundamental changes in chemical use and manufacture, referred to as primary prevention or inherent safety.

In the U.S., concern about chemical accidents after the Bhopal disaster led to the passage of the 1986 Emergency Planning and Community Right-to-Know Act. The EPCRA requires local emergency planning efforts throughout the country, including emergency notifications. The law also requires companies to make publicly available information about their storage of toxic chemicals. Based on such information, citizens can identify the vulnerable zones in which severe toxic releases could cause harm or death.

In 1990, the U.S. Chemical Safety and Hazard Investigation Board was established by Congress, though the CSB did not become operational until 1998. The Board’s mission is to determine the root causes of chemical accidents and issue safety recommendations to prevent future accidents.

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Chemical change

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Chemical change

A chemical change is a process in which reactants are changed into one or more different products. A chemical change occurs whenever new compounds are formed or existing compounds decomposed. During this reaction, chemical bonds between atoms are broken and new chemical bonds formed. This results in a rearrangement of the chemical bonds.

There are several different types of chemical change. These include synthesis, decomposition, single displacement, double displacement, neutralization, precipitation and redox.

Indicators of a chemical change include a colour change, the formation of a precipitate, the formation of gas, production of heat or light, the appearance of a new substance, a use-up of a starting substance or a change in temperature or energy. When new substances are formed, a chemical change has occurred, and a chemical reaction has taken place.

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Chemical equation

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Chemical equation

A chemical equation is a symbolic representation of a chemical reaction. It is a formula used to display different stages for chemical reactions, where chemical substances are changed into other substances. The elements and/or compounds to the left of the arrow in a chemical equation represent the reactants, the arrow represents the transition stage, and the species to the right of the arrow represent the products. The four basic chemical equations are:

A → B
A → B + C
A + B → C
A + B → B + C

For example, the combustion of methane in oxygen is depicted as:

CH4 + 2 O2 → CO2 + 2 H2O,

and the reversible reaction of the Haber process is shown as

N2(g) + 3H2(g) 2NH3(g) + ΔH.

A chemical equation should represent the stoichiometry observed in the chemical reaction. When the net amount of atoms on both sides of the equation is identical the equation is said to be a balanced equation.

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Reading chemical equations

When reading a chemical equation there are some points to consider.

  • Each side of an equation represents a mixture of chemicals. The mixture is written as a set of molecular formulas, separated by + symbols.
  • Each formula is preceded by an optional scalar number (if no scalar number is written, it is implied that the number is 1). The scalar numbers indicate the relative quantity of molecules in the reaction. For instance, the string 2H2O + 3CH4 represents a mixture containing 2 molecules of H2O for every 3 molecules of CH4.
  • The two sides of the equation are separated by an arrow. If the reaction is non-reversible, a right-arrow (→) is used, indicating that the left side represents the mixture of chemicals before the reaction, and the right side indicates the mixture after the reaction. For a reversible reaction, a two-way arrow is used. For example the equation 4Na + O2 → 2Na2O represents a non-reversible reaction. In this reaction, sodium (Na) and oxygen (O2) are converted to a single molecule, Na2O (containing 2 sodium atoms and 1 oxygen atom). We can also see that for every 4 sodium atoms at the beginning of the reaction, a single O2 molecule will participate, and 2 Na2O molecules will result.
  • A chemical equation does not imply that all reactants are consumed in a chemical process. For instance a limiting reagent determines how far a reaction can go.
  • In an ionic equation balancing of charge also takes place. In a full equation all reacts are written as molecules.

Balancing chemical equations

In a chemical reaction, the quantity of each element does not change. Thus, each side of the equation must represent the same quantity of any particular element. Also in case of net ionic reactions the same charge must be present on both sides of the equation. Then, and only then, the equation is balanced. Given an unbalanced equation, one may balance it by changing the scalar number for each molecular formula.

Simple chemical equations can be balanced by inspection, that is, by trial and error. Generally, it is best to balance the most complicated molecule first. Hydrogen and oxygen are usually balanced last.

Ex #1. Na + O2 → Na2O

In order for this equation to be balanced, there must be an equal amount of Na on the left hand side as on the right hand side. As it stands now, there is 1 Na on the left but 2 Na’s on the right. This problem is solved by putting a 2 in front of the Na on the left hand side:

2Na + O2 → Na2O

In this equation there are 2 Na atoms on the left and 2 Na atoms on the right. In the next step the oxygen atoms are balanced as well. On the left hand side there are 2 O atoms and the right hand side only has one. This is still an unbalanced equation. To fix this a 2 is added in front of the Na2O on the right hand side. Now the equation reads:

2Na + O2 → 2Na2O

Notice that the 2 on the right hand side is “distributed” to both the Na2 and the O. Currently the left hand side of the equation has 2 Na atoms and 2 O atoms. The right hand side has 4 Na’s total and 2 O’s. Again, this is a problem, there must be an equal amount of each chemical on both sides. To fix this 2 more Na’s are added on the left side. The equation will now look like this:

4Na + O2 → 2Na2O

This equation is a balanced equation because there is an equal amount of element’s on the left and right hand sides of the equation.

Ex #2. P4 + O2 → P4O10

This equation is not balanced because there is an unequal amount of O’s on both sides of the equation. The left hand side has 4 P’s and the right hand side has 4 P’s. So the P atoms are balanced. The left hand side has 2 O’s and the right hand side has 10 O’s. To fix this unbalanced equation a 5 in front of the O2 on the left hand side is added to make 10 O’s on both sides resulting in

P4 + 5O2 → P4O10

The equation is now balanced because there is an equal amount of substances on the left and the right hand side of the equation.

Ex #3. C2H5OH + O2 → CO2 + H2O

This equation is more complex than the previous examples and requires more steps. The most complicated molecule here is C2H5OH, so balancing begins by placing the coefficient 2 before the CO2 to balance the carbon atoms.

C2H5OH + O2 → 2CO2 + H2O

Since C2H5OH contains 6 hydrogen atoms, the hydrogen atoms can be balanced by placing 3 before the H2O:

C2H5OH + O2 → 2CO2 + 3H2O

Finally the oxygen atoms are balanced. Since there are 7 oxygen atoms on the right and only 3 on the left, a 3 is placed before O2, to produce the balanced equation:

C2H5OH + 3O2 → 2CO2 + 3H2O

Linear system balancing

In reactions involving many compounds, balancing may get harder, in that situation one can try balancing using a linear system:

1. Assign variables to each coefficient:

  • a K4Fe(CN)6 + b H2SO4 + c H2O → d K2SO4 + e FeSO4 + f (NH4)2SO4 + g CO

2. We must have the same quantities of each atom in each side of the equation. So, for each element, count its atoms and equal both sides:

  • K: 4a = 2d
  • Fe: 1a = 1e
  • C: 6a = g
  • N: 6a = 2f
  • H: 2b+2c = 8f
  • S: b = d+e+f
  • O: 4b+c = 4d+4e+4f+g

3. Solving the system(usually direct substitution is the best way)

  • d=2a
  • e=a
  • g=6a
  • f=3a
  • b=6a
  • c=6a

which means that we have all coefficients depending on a parameter a, just choose a=1(a number that will make all of them small whole numbers) and you’ll have:

  • a=1 b=6 c=6 d=2 e=1 f=3 g=6

4. And the balanced equation at last:

  • K4Fe(CN)6 + 6 H2SO4 + 6 H2O → 2 K2SO4 + FeSO4 + 3 (NH4)2SO4 + 6 CO

To speed up the process, one can combine both methods to get a more practical algorithm:

1. Identify elements which occur in one compound in each member(this is very usual)

2. Start with the one among those which has a big index(this will help to keep working with integers), and assign a variable, let’s say a.

  • a K4Fe(CN)6 + H2SO4 + H2O → K2SO4 + FeSO4 + (NH4)2SO4 + CO

3. Well, K2SO4 has to be 2a(because of K), and also, FeSO4 has to be 1a(because of Fe), CO has to be 6a(because of C) and (NH4)2SO4 has to be 3a(because of N). Well, this takes out the first four equations of the system! We already now that, whatever the coefficients are, those proportions must hold:

  • a K4Fe(CN)6 + H2SO4 + H2O → 2a K2SO4 + a FeSO4 + 3a (NH4)2SO4 + 6a CO

4. We can continue by writing the equations now(and having simpler problem to solve) or, in this particular case(although not so particular) we could continue by noticing that adding the Sulfurs we get 6a for H2SO4 and finally by adding the hydrogens(or the oxygens) we get the lasting 6a for H2SO4.

5. Again, having a convenient value for a(in this case 1 will do, but if a gets fractionary values in the other coefficients you will like to cancel the denominators) we get the result:

  • K4Fe(CN)6 + 6 H2SO4 + 6 H2O → 2 K2SO4 + FeSO4 + 3 (NH4)2SO4 + 6 CO

External links

Chemical industry

Filed under: Chemistry Terms — @ 8:55 am

Chemical industry

Chemical tanks in Lillebonne, France

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Chemical tanks in Lillebonne, France

The chemical industry refers to industry involved in the production of chemicals with high economic impact. These include petrochemicals, agrochemicals, pharmaceuticals, polymers, paints, and oleochemicals. Chemical processes are used, including chemical reactions to form new substances, separations based on properties such as solubility or ionic charge, and distillations, in addition to transformations by heating and other methods.

Chemical industries involve the processing of, or change in, raw materials obtained by mining, and agriculture among other supply sources, into materials and substances that are useful on their own, or in other industries. The food processing industries are generally not included in the term “chemical industry”.

Companies

The biggest companies in chemical industry on Earth are listed with business volume in billions of Euros.

  • Badische Anilin- und Soda-Fabrik (BASF)(D) 28 (formerly IG-Farben)
  • Dow Chemical (USA) 27
  • DuPont (USA) 24
  • Bayer (D) 20 (formerly IG-Farben)
  • ExxonMobil Chemicals (USA) 20 (formerly Standard Oil)
  • Atofina (F) 20
  • BP Chemicals (GB) 13
  • Mitsubishi Chemicals (J) 12
  • Deutsche Gold- und Silber-Scheide-Anstalt (DEGUSSA)(D) 11(formerly IG-Farben)
  • Shell Chemicals (NL/GB) 11

Chemical law

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Chemical law

Chemical laws are those laws of nature relevant to chemistry. The most fundamental concept in chemistry is the law of conservation of mass, which states that there is no detectable change in the quantity of matter during an ordinary chemical reaction. Modern physics shows that it is actually energy that is conserved, and that energy and mass are related; a concept which becomes important in nuclear chemistry. Conservation of energy leads to the important concepts of equilibrium, thermodynamics, and kinetics.

Further laws of chemistry elaborate on the law of conservation of mass. Joseph Proust’s law of definite composition says that pure chemicals are composed of elements in a definite formulation; we now know that the structural arrangement of these elements is also important.

Dalton’s law of multiple proportions says that these chemicals will present themselves in proportions that are small whole numbers (i.e. 1:2 O:H in water); although in many systems (notably biomacromolecules and minerals) the ratios tend to require large numbers, and are frequently represented as a fraction. Such compounds are known as non-stoichiometric compounds

More modern laws of chemistry define the relationship between energy and transformations.

  • In equilibrium, molecules exist in mixture defined by the transformations possible on the timescale of the equilibrium, and are in a ratio defined by the intrinsic energy of the molecules—the lower the intrinsic energy, the more abundant the molecule.
  • Transforming one structure to another requires the input of energy to cross an energy barrier; this can come from the intrinsic energy of the molecules themselves, or from an external source which will generally accelerate transformations. The higher the energy barrier, the slower the transformation occurs.
  • There is a hypothetical intermediate, or transition structure, that corresponds to the structure at the top of the energy barrier. The Hammond-Leffler Postulate states that this structure looks most similar to the product or starting material which has intrinsic energy closest to that of the energy barrier. Stabilizing this hypothetical intermediate through chemical interaction is one way to achieve catalysis.
  • All chemical processes are reversible (law of microscopic reversibility) although some processes have such an energy bias, they are essentially irreversible.

Chemical reaction

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Chemical reaction

A chemical reaction is a process that results in the interconversion of chemical substances [1]. The substance or substances initially involved in a chemical reaction are called reactants. Chemical reactions are characterized by a chemical change and it yields one or more products which are different from the reactants. Classically, chemical reactions encompass changes that strictly involve the motion of electrons in the forming and breaking of chemical bonds, although the general concept of a chemical reaction, in particular the notion of a chemical equation, is applicable to transformations of elementary particles, as well as nuclear reactions.

Many different chemical reactions are used in combinations in chemical synthesis in order to get a desired product. In biochemistry, series of chemical reactions form metabolic pathways, since straight synthesis of a product would be energetically impossible in conditions within a cell. Chemical reactions are also divided into organic reactions and inorganic reactions.

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Reaction types

Chemical reactions may be classified in different ways depending on the particular aspect considered for elaborating the division, or on the branch of Chemistry which the classification originates from. Some examples of widely used terms for describing common kinds of reactions are:

  • Isomerisation, in which a chemical compound undergoes a structural rearrangement without any change in its net atomic composition; see stereoisomerism
  • Direct combination or synthesis, in which two or more chemical elements or compounds unite to form a more complex product:
2H2 (g) + O2 (g) → 2H2O (l)
  • Chemical decomposition or analysis, in which a compound is decomposed into smaller compounds or elements:
2H2O (l) → 2H2 (g) + O2(g)
  • Single displacement or substitution, characterized by an element being displaced out of a compound by a more reactive element:
2Na(cr) + 2HCl (aq) → 2NaCl (aq) + H2 (g)
  • Double displacement or coupling substitution , in which two compounds in aqueous solution (usually ionic) exchange elements or ions to form different compounds:
NaCl (aq) + AgNO3 (aq) → NaNO3 (aq) + AgCl (s)
  • Combustion, in which any combustible substance combines with an oxidizing element, usually oxygen, to generate heat and form oxidized products. The term combustion is used usually only for reactions that destroy complex molecules, i.e. a controlled oxidation of a single functional group is not combustion.
C10H8 (g) + 14O2 (g) → 10CO2 (g) + 4H2O (g) + heat
CH2S + 6 F2CF4 + 2 HF + SF6 + heat

Some branches of chemistry include any minor changes in chemical conformation in the reaction types, while others consider these changes merely as physical properties of a compound.

The collision of more than two particles into the ordered structure necessary to perform chemical transformations is extremely unlikely; which is why ternary reactions in practice are not observed. A chemical reaction may require three or more reagents, but the process can generally be decomposed into a stepwise series or a set of stepwise reactions of the above.

The large diversity of chemical reactions makes it difficult to establish simple criteria for functional (as opposed to mechanistic) classification. However, some kinds of reactions have similarities which make it possible to define some larger groups. A few examples are:

  • Organic reactions encompass several different kinds of reactions involving compounds which have carbon as the main element in their molecular structure. These reactions occur mostly according to, within, by, or via functional groups.
  • Petrochemical reactions are often distinguished from other organic reactions.
  • Redox reactions involve augmenting or decreasing the electrons associated with a particular atom. according to its oxidation number.
  • Combustion, in which a substance reacts with an oxidizing element, such as oxygen gas.

Reactions are also classified according to their mechanism:

  • Reactions of ions, e.g. disproportionation of hypochlorite
  • Reactions with reactive ionic intermediates, e.g. reactions of enolates
  • Radical reactions, e.g. combustion at high temperature
  • Reactions of carbenes

Thermochemistry

See main article: Thermochemistry.

Thermochemistry deciphers whether a specific chemical reaction can or cannot occur. Thermodynamics (or what is now known as equilibrium thermodynamics) understands the reaction in terms of the initial and final states of the reaction mixture.

Reactions very seldom occur directly. Usually, reactants must collide to form an activated complex. This complex has a higher internal energy than the original reactants combined, having gained some from the kinetic energy of the reactant substances’ collision. This energy allows for the rearrangement of bonds which constitutes the reaction. In some reactions, the reactants may pass through several reactive intermediates before becoming products.

Thermodynamics does not attempt to figure out the process by which a reaction occurs. This field of study is taken up by the field of chemical kinetics. Another question “How fast is the reaction?” is also left completely unanswered by it. Chemical kinetics attempts to put all these phenomena into perspective.

Chemical equilibrium

Every chemical reaction is, in theory, reversible. In a forward reaction the substances defined as reactants are converted to products. In a reverse reaction products are converted into reactants.

Chemical equilibrium is the state in which the forward and reverse reaction rates are equal, thus preserving the amount of reactants and products. However, a reaction in equilibrium can be driven in the forward or reverse direction. This is done by changing the reaction conditions such as temperature or pressure. Le Chatelier’s principle can be used to predict whether products or reactants will be formed.

Although all reactions are reversible to some extent, some reactions can be classified as irreversible. An irreversible reaction is one that “goes to completion.” This phrase means that nearly all of the reactants are used to form products. These reactions are very difficult to reverse even under extreme conditions.

Exothermic reactions

A sketch of an exothermic reaction

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A sketch of an exothermic reaction

According to energy balance criteria, that is, chemical reaction equilibria criteria, any closed system will tend to minimize its free energy. Without any outside influence, any reaction mixture, too, will try to do the same. For many cases, an analysis of the enthalpy of the system will give a decent account of the energetics of the reaction mixture. The enthalpy of a reaction is calculated using standard reaction enthalpies and the Hess’ law of constant heat summation. Many of these enthalpies may be found in beginners’ books on thermodynamics. For example, consider the combustion of methane in oxygen:

CH4 + 2 O2 → CO2 + 2 H2O

By calculating the amounts of energy required to break all the bonds on the left (”before”) and right (”after”) sides of the equation using collected data, it is possible to calculate the energy difference between the reactants and the products. This is referred to as ΔH, where Δ (Delta) means difference, and H stands for enthalpy, a measure of energy which is equal to the heat transferred at constant pressure. ΔH is usually given in units of kilojoules (kJ) or in kilocalories (kcal).

If ΔH is negative for the reaction, then energy has been released often in the form of heat. This type of reaction is referred to as an exothermic reaction (literally, outside heat, or throwing off heat). An exothermic reaction is more favourable and thus more likely to occur. An example reaction is combustion, known from everyday experience, since burning gas in air produces heat.

Endothermic reactions

A reaction may have a positive ΔH. If a reaction has a positive ΔH, it consumes energy as the reaction moves towards completion. This type of reaction is called an endothermic reaction (literally, inside heat, or absorbing heat).

The above rule, “Exothermic reactions are favourable”, is usually true. However, there may be situations where exothermic reactions may not be favourable. This happens when the stability obtained due to loss of enthalpy is off set by a corresponding decrease in entropy (a measure of disorder). The exact rule is that a reaction is favourable when the Gibbs free energy of that reaction is negative where ΔG = ΔHTΔS; ΔG being the change in Gibbs free energy, ΔH being the change in enthalpy, and ΔS is the change in entropy

A reaction is called spontaneous if its thermodynamically favoured, by that meaning that it causes a net increase on entropy. Spontaneous reactions (in opposition to non-spontaneous reactions) do not need external perturbations (such as energy supplement) to happen. In a system at chemical equilibrium, it is expected to have larger concentrations of the substances formed by the spontaneous direction of the process.

Thus, in a global isolated system (which it strictly isn’t, see entropy), spontaneous reactions may be understood to occur without human interference. Most spontaneus reactions in this system are exothermic (such as rusting) or metamorphism, thus increasing the global entropy, though photosynthesis is an important exception (in a global system).

Chemical kinetics

See main article: Chemical kinetics.

The rate of a chemical reaction is a measure of how the concentration of the involved substances changes with time. Analysis of reaction rates is important for several applications, such as in chemical engineering or in chemical equilibrium study. Rates of reaction depends basically on:

  • Reactant concentrations, which usually make the reaction happen at a faster rate if raised,
  • Surface Area, the amount of the substance being used,
  • Pressure, By increasing the pressure, you squeeze the molecules together so you will increase the frequency of collisions between the molecules.
  • Activation energy, which is defined as the amount of energy required to make the reaction start and carry on spontaneously. Higher activation energy implies that a reaction will be harder to start and, therefore, slower.
  • Temperature, which hastens reactions if raised, because higher temperature means that the involved species will have more energy, thus making the reaction easier to happen,
  • The presence or absence of a catalyst. Catalysts are substances which change the pathway (mechanism) of a reaction which in turn increases the speed of a reaction by lowering the activation energy needed for the reaction to take place. A catalyst is not destroyed or changed during a reaction, so it can be used again.

Reaction rates are related to the concentrations of substances involved in reactions, as quantified by the law of mass action. Reactions whose rates are independent of reactant concentrations are called zero-order reactions.

See also

  • List of reactions
  • List of publications in chemistry

External links

References

  1. IUPAC Gold Book Definition

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