Crystal Systems

Crystal Systems

Arrangements for stacking spheres, each one characterized by a packing efficiency (percentage of total volume occupied by spheres)

1) Simple cubic unit cell
8 atoms define corners – atoms touch along edges, but not along diagonal
Coordination # = 6. 4 in layer, 1 above, 1 below
1 atom/unit cell (1/8 ´ 8 atoms)
















2) Body-centered cubic unit cell
8 atoms define corners plus one in center – atoms touch central atom, not each other
Coordination # = 8. 4 above and 4 below.
2 atoms/unit cell (1/8 ´ 8 atoms + 1 atom in center)

























3) Face-centered cubic unit cell
8 atoms define corners plus 6 in center of each face – Corner atoms touch face atom, not each other
Coordination # = 12. 4 in layer, 1 above, 1 below, 6 faces
4 atoms/unit cell (1/8 ´ 8 crnr atoms + ½ ´ 6 face atoms)

Karbon Dioksida, Misteri Sebuah Senyawa

Fakta tentang karbon dioksida

Karbon dioksida atau CO2, semua orang mengenal senyawa ini sebagai gas, tak berbau, tak berwarna, tak beracun dan berasal dari setiap mekanisme pembakaran maupun metabolisme. Gas Karbon dioksida pertama kali diamati keberadaannya oleh Van Helmont, tahun 1577. Secara statistik alamiah, gas ini tidak melimpah di muka bumi dan konstan persentasenya. Sejak lama orang tidak memberi perhatian terhadap sifat-sifat gas tersebut. Pemanfaatan gas CO2 salah satunya adalah dapat diubah fasenya menjadi padat dan disebut “dry ice“, digunakan dalam industri pengawetan hingga industri film maupun sinetron (memberi efek kabut di film serem atau sinetron misteri).

Cerita dibalik si misterius CO2

Lalu mengapa sekarang orang-orang terutama ilmuwan meributkan gas tak bersalah ini ??! Sebenarnya gas CO2 memang tak bersalah, tapi kitalah yang membuat kesalahan. Perkembangan ilmu pengetahuan dan teknologi sering kali tidak sejalan dengan kehendak alam. Sejak dimulainya revolusi industri di Inggris hingga revolusi telekomunikasi jaman sekarang telah terjadi peningkatan persentase CO2 di muka bumi akibat aktivitas produksi dan konsumsi. Mulailah dikenal istilah “Green House Effect“, yaitu meningkatnya kadar CO2 di atmosfer menjadikan bumi tambah panas, memberikan efek “Global Warming” dan selanjutnya “Global Climate Change“. Lha, apa hubungan CO2 dengan panas ?, Begini, Karena kebetulan sifat CO2 yang menyerap energi panas dari radiasi sinar infra merah yang dipancarkan matahari, akibatnya makin terakumulasilah energi panas tersebut dimuka bumi bahkan bisa mencairkan es kutub lho ! Ditambah lagi penggunaan senyawa CFC (Chloro Fluoro Carbon) sebagai pelarut, material gas pendingin dalam refrigerator dan foaming agent dalam industri polimer ternyata malah “memakan” ozone yang melindungi bumi dari radiasi sinar ultra violet matahari yang berenergi tinggi. Ironisnya fakta lain tentang CFC menjadikan orang tetap menggunakan CFC, yaitu dia ternyata gas yang tidak terlalu berbahaya terhadap mahluk hidup, tidak mudah terbakar, dan punya sifat-sifat unik karena variasi kandungan atom klor dan fluornya. Tapi bumi sudah panas ditambah lagi bumi semakin terbuka terhadap pancaran energi tinggi UV yang mematikan, menjadikan kalangan terutama para ilmuwan kalang kabut mencari solusi agar bumi ini tetap menjadi tempat yang nyaman dihuni paling tidak sampai menjelang kiamat.

Sejelek-jeleknya CO2, masih lebih jelek orang yang tidak perduli lingkungan dan hanya mengeruk keuntungan dengan menyiksa alam serta korupsi gila-gilaan. Yang paling menderita dari dampak di atas adalah penduduk bumi awam yang tidak mengerti apa-apa, padahal kita punya hak hidup yang sama. Nah, patutlah kita cukup berterima kasih kepada beberapa ilmuwan yang mencurahkan hidupnya bagi penyelamatan bumi ini. Akhirnya ditemukan fakta-fakta lain dari CO2 yang kemungkinan bisa dimanfaatkan demi kebaikan.

Apa to kebaikan CO2 ituh ?

Akhir-akhir ini mulai luas dikenal istilah “Green Chemistry” atau lebih menarik lagi “Green, Benign and Sustainable Chemistry“. Istilah itu sebenarnya adalah gerakan pembaharuan dalam dunia riset dipelopori oleh para ilmuwan setengah gila yang melawan arus aliran trend riset, karena pada awalnya riset lebih banyak berkutat pada eksploitasi sumber daya bumi daripada menyelamatkannya. Seiring dengan semakin ditekannya penggunaan material CFC sebagai pelarut, maka dicarilah alternatif pengganti yang memiliki sitaf-sifat serupa tapi lebih ramah terhadap lingkungan. Mulailah ilmuwan melirik manfaat lain dari CO2 dari sekedar gas tak berdosa menjadi gas yang tak berdosa sekaligus bermanfaat yaitu sebagai pelarut superkritis. CO2 sebagai fluida superkritis ??? Wah, buat kita-kita yang awam mungkin sulit membayangkan, nah akan diulas sedikit tentang sifat-sifatnya. CO2 sebagai fluida superkritis sebenarnya adalah gas yang dinaikkan temperaturnya mencapai temperatur kritis (temperatur tertinggi yang dapat mengubah fase gas menjadi fase cair dengan cara menaikkan tekanan), dan memiliki tekanan kritis (tekanan tertinggi yang dapat mengubah fase cair menjadi fase gas dengan cara menaikkan temperatur) sehingga sifat-sifatnya berada di antara sifat gas dan cairan. Nah, bingung bukan ??! Biar lebih jelas silahkan lihat diagram supercritical fluids (SCF) ini.

Sebagai pelarut superkritis, CO2, telah cukup banyak dimanfaatkan dibidang penelitian dan industri. Keuntungan lain adalah kita tidak perlu membuat CO2 melainkan cukup menyaringnya dari udara sekitar kita. Walaupun teknologinya masih mahal, bukan berarti tidak bisa dimanfaatkan secara nyata. Dibidang isolasi dan pengolahan bahan alam, CO2 superkritis dimanfaatkan sebagai pelarut dalam proses ekstraksi maupun de-ekstraksi senyawa-senyawa aktif dari tumbuhan untuk pengobatan, atau senyawa-senyawa penting untuk industri makanan, misalnya ekstraksi minyak atsiri lemon, jahe, beta-carotene dari tumbuh-tumbuhan atau de-ekstraksi caffein pada kopi. Namun pengembangan lebih lanjut rupanya masih terhambat oleh miskinnya pengetahuan tentang sifat-sifat maupun fasa-fasa campuran CO2 superkritis dengan bahan terlarut dan perilaku senyawa terlarut di dalamnya.

Dibidang pertambangan minyak bumi, bahkan penggunaan CO2 yang dicairkan sangat besar. Fluida ini dialirkan ke dalam sumber-sumber minyak yang mulai menipis cadangannya untuk mengangkat cadangan minyak tersisa. Masalah utamanya adalah fluida ini kekentalannya rendah sehingga tidak mampu mengangkat minyak secara maksimum. Pengembangan aditif yang mampu meningkatkan kekentalan (viscosity) fluida CO2 belum mampu bekerja optimum karena kelarutan aditif-aditif tersebut yang sulit diperkirakan.

Suatu perkembangan lebih menggembirakan dalam industri polimer kembali mengangkat kepopuleran CO2. Dupont, sebuah perusahan terkemuka dalam inovasi industri kimia telah mampu memproduksi semacam busa atau dikenal ‘foamed thermoplastic’ yang populer disebut ‘fluoropolimer’ berkat ditemukannya polimer ‘perfluoroalkil akrilat’ oleh Desimone dan rekan tahun 1992. Fluoropolimer ini benar-benar larut dalam CO2 setelah sebelumnya digunakan pelarut dan surfaktan berbasis fluor. Permasalahannya adalah pengembangan ‘foamed polymer’ yang benar-benar menggunakan CO2 sebagai agen pembuih tidak terlalu berhasil. Walaupun Dow, suatu perusahaan terkemuka juga dibidang industri polimer, telah memproduksi polistiren berbasis keseluruhan CO2 sebagai agen pengembang, namun muncul kesulitan teknis lain dalam polimer berbasis keseluruhan CO2, misalnya pecahnya gelembung akibat cepatnya difusi CO2 di dalam larutan polimer atau soal bagaimana membuat polimer yang memiliki daya hantar panas rendah.

Sesungguhnya masih banyak kegunaan yang bisa digali dari gas CO2 sebagai material ramah lingkungan. Misalnya dalam industri pelapisan material menggunakan polimer yang dapat larut dalam CO atau pembuatan partikel koloid dalam industri farmasi menggunakan pelarut CO2. Kenyataan bahwa gas CO, O2 dan H2 benar-benar dapat bercampur dan larut dalam CO2 sebenarnya memberikan kemungkinan untuk melakukan reaksi karbonilasi, oksidasi maupun hidrogenasi dalam pelarut CO2. Namun kendala dalam aplikasi teknologi-teknologi tersebut secara massal membuat kaum industriawan masih enggan untuk benar-benar beralih menggunakan CO2.


http://sudarmono-kimia-anorganik.blogspot.com/

Molecular Orbital Diagram for H-F

Molecular Orbitals for Heterogeneous Diatomic Molecules
A simple approach to molecular orbital (MO) theory for heterogeneous diatomic molecules is to show the energy level diagram.

Molecular Orbital Diagram for H-F
Interaction occurs between the 1s orbital on hydrogen and the 2p orbital in fluorine causing the formation of a sigma-bonding and a sigma-antibonding molecular orbital, as shown below




http://www.science.uwaterloo.ca/~cchieh/cact/applychem/mohetro.html

Characteristic structures of ionic solids

Metals have structures which may be discussed in terms of the close packing of spheres, and as a result have the high coordination numbers of the close packed systems. Ionic solids, however, have lower coordination numbers, and the discussion of the structure simply in terms of close packed species has to be adapted.

The idea of an ionic solid, though, depends on being able to define an ion. The Ionic Model treats a solid as being made up of oppositely charged spheres that interact by the coulombic forces between them, and the short range repulsive forces which occur between closed shell species at small separations.


The use of the idea of close packed spheres, and the holes within these structures is very useful in the discussion of the structures of ionic solids.

The structures of many ionic solids of the formula AB and AB2 may be visualized in terms of the close packed arrangement of the negatively charged anions, with the positively charged cations occupying the holes within the structure.

Characteristic structures of ionic solids

The simple structures come from the arrangement of the anions (though sometimes the cations) in the positions of the spheres in the fcc or hcp lattices, and the cations go into some or all of the octahedral and tetrahedral holes within the lattices.

Structures based on face centered cubic lattices

The Rock Salt structure


This the structure adopted by Sodium Chloride, NaCl. It is based on the fcc array of the large chloride anions, and the sodium cations occupy all the octahedral holes in the fcc lattice. However, it could also be seen as an fcc array of sodium ions, with the anions in all the octahedral holes.

Each ion is octahedrally coordinated by six counterions, and so this structure has so-called (6,6)-coordination, where the first number refers to the coordination of the cation and the second to the anion.

The structure beyond the first coordination sphere can also be visualized.


The extended coordination of the ions can be seen by considering the coordination of the sodium ion at the center of the unit cell. It has six nearest neighbours, which are the oppositely charged chloride anions, octahedrally arranged at the centers of the faces of the cube. The next nearest neighbours are 12 sodium cations, sited on the middle of each of the edges of the cube. Beyond that, there are 8 chloride anions situated at the corners of the cube.

The Sphalerite structure

This is the structure adopted by Zinc Sulphide, ZnS, and is also known as the zinc blende structure.

Here there is an fcc array of sulphide anions, and the zinc cations occupy half the tetrahedral holes. There are two tetrahedral holes for each atom in the fcc array, and so the stoichiometry of the compound dictates that only half of them be occupied, so that there are the same number of cations as anions.

The cations are tetrahedrally coordinated by anions, and the anions are surrounded by eight tetrahedral sites, of which half are occupied, and hence the anions are also four-coordinate. The zinc blende structure therefore has (4,4)-coordination.


The Fluorite structure

This is the structure adopted by Calcium Fluoride, CaF2.

There is now an fcc array of calcium cations, and the fluoride anions occupy all of the tetrahedral holes. There are two tetrahedral holes for each atom in the fcc array, and so the stoichiometry of the compound dictates that both of the tetrahedral holes be occupied for each of the cationic fcc sites.

The anions are tetrahedrally coordinated by cations, and the cations are surrounded by eight tetrahedral sites, all of which are occupied, and hence the cations are eight-coordinate. The fluoride structure therefore has (8,4)-coordination.



The antifluorite structure is that adopted by compounds with the stoichiometry A2B, where A is the cation and B is the anion. Examples include potassium oxide, K2O. Here, the fcc array of oxide ions has potassium ions in all the tetrahedral holes, and there is a (4,8)-coordination.

Structures based on other cubic lattices

The Caesium Chloride structure

This is the structure adopted by Caesium Chloride, CsCl, and also by CsBr and CsI. It is formed when the anion and cation have similar sizes.

This is based on a simple cubic lattice of anions. In this the anions are not close packed, but the unit cell is a simple cube with an ion at the each of the corners. The cations are located at the center of the anionic cube.

Similarly, the structure can be considered as a simple cubic array of cations with the anions at the center of the cubes. It is fully understood as interleaved simple cubic lattices of cations and anions.


The anions, at the corners of the cube, are coordinated to eight cations at the centers of each of the surrounding cubes, and the cations are surrounded by the eight anions at the corners of the cube. The cesium chloride structure therefore has (8,8)-coordination.


The Perovskite Structure

This is the structure adopted by Calcium Titanate, CaTiO3. It is the template for many compounds of the formula ABX3.

In this structure, there is a simple cubic array of B atoms (Ti), with the A atoms (Ca) occupying the center of the cube, as in CsCl, and the X atoms (O) being sited at the center of the 12 edges of the simple cube.

Therefore, the central A ion is coordinated by 12 X ions; the B ion is octahedrally coordinated by 6 X ions; and the X ion is linearly coordinated by 2 B ions.




Structures based on hexagonal close packed lattices

The Wurtzite Structure

This is another structure adopted by Zinc Sulphide, ZnS, the difference from Zinc Blende being that the ions now occupy the sites in an hcp lattice.

Here there is an hcp array of sulphide anions, and the zinc cations occupy half the tetrahedral holes. There are two tetrahedral holes for each atom in the hcp array, and so the stoichiometry of the compound dictates that only half of them be occupied, so that there are the same number of cations as anions.



The cations are tetrahedrally coordinated by anions, and the anions are also tetrahedrally coordinated by cations. The Wurtzite structure therefore has (4,4)-coordination.

The local coordination of the ions at the next nearest neighbour level is the same in Wurtzite as Sphalerite, each ion being tetrahedrally coordinated by its counterions, but the coordination differs at the next nearest neighbour level.

The Nickel Arsenide Structure

This is the structure of NiAs, and is based on a distorted hcp array of Arsenide anions. By contrast with the wurtzite structure, however, which is also of formula AB, the cations now occupy all the octahedral sites rather than half the tetrahedral holes. There is one octahedral hole for each hcp lattice site, and so the AB stoichiometry is preserved.


The local coordination of the anions and cations are different in this structure.



http://www.everyscience.com/Chemistry/Inorganic/Ionic_Solids/b.1297.php

Hair Color Chemistry

The first safe commercial haircolor was created in 1909 by French chemist Eugene Schuller, using the chemical paraphenylenediamine. Hair coloring is very popular today, with over 75% of women coloring their hair and a growing percentage of men following suit. How does haircolor work? It's the result of a series of chemical reactions between the molecules in hair, pigments, as well as peroxide and ammonia, if present.

What is Hair?

Hair is mainly keratin, the same protein found in skin and fingernails. The natural color of hair depends on the ratio and quantities of two other proteins, eumelanin and phaeomelanin. Eumelanin is responsible for brown to black hair shades while phaeomelanin is responsible for golden blond, ginger, and red colors. The absence of either type of melanin produces white/gray hair.

Natural Colorants

People have been coloring their hair for thousands of years using plants and minerals. Some of these natural agents contain pigments (e.g., henna, black walnut shells) and others contain natural bleaching agents or cause reactions that change the color of hair (e.g., vinegar). Natural pigments generally work by coating the hair shaft with color. Some natural colorants last through several shampoos, but they aren't necessarily safer or more gentle than modern formulations. It's difficult to get consistent results using natural colorants, plus some people are allergic to the ingredients.

Temporary Hair Color

Temporary or semi-permanent haircolors may deposit acidic dyes onto the outside of the hair shaft or may consist of small pigment molecules that can slip inside the hair shaft, using a small amount of peroxide or none at all. In some cases, a collection of several colorant molecules enter the hair to form a larger complex inside the hair shaft. Shampooing will eventually dislodge temporary hair color. These products don't contain ammonia, meaning the hair shaft isn't opened up during processing and the hair's natural color is retained once the product washes out.

How Lightening Works

Bleach is used to lighten hair. The bleach reacts with the melanin in hair, removing the color in an irreversible chemical reaction. The bleach oxidizes the melanin molecule. The melanin is still present, but the oxidized molecule is colorless. However, bleached hair tends to have a pale yellow tint. The yellow color is the natural color of keratin, the structural protein in hair. Also, bleach reacts more readily with the dark eumelanin pigment than with the phaeomelanin, so some gold or red residual color may remain after lightening. Hydrogen peroxide is one of the most common lightening agents. The peroxide is used in an alkaline solution, which opens the hair shaft to allow the peroxide to react with the melanin.

Permanent Hair Color

The outer layer of the hair shaft, its cuticle, must be opened before permanent color can be deposited into the hair. Once the cuticle is open, the dye reacts with the inner portion of the hair, the cortex, to deposit or remove the color. Most permanent hair colors use a two-step process (usually occurring simultaneously) which first removes the original color of the hair and then deposits a new color. It's essentially the same process as lightening, except a colorant is then bonded within the hair shaft. Ammonia is the alkaline chemical that opens the cuticle and allows the hair color to penetrate the cortex of the hair. It also acts as a catalyst when the permanent hair color comes together with the peroxide. Peroxide is used as the developer or oxidizing agent. The developer removes pre-existing color. Peroxide breaks chemical bonds in hair, releasing sulfur, which accounts for the characteristic odor of haircolor. As the melanin is decolorized, a new permanent color is bonded to the hair cortex. Various types of alcohols and conditioners may also be present in hair color. The conditioners close the cuticle after coloring to seal in and protect the new color.
http://chemistry.about.com/od/howthingswork/a/fireworks.htm

How Fireworks Work

Fireworks have been a traditional part of New Year's celebrations since they were invented by the Chinese almost a thousand years ago. Today fireworks displays are seen on most holidays. Have you ever wondered how they work? There are different types of fireworks. Firecrackers, sparklers, and aerial shells are all examples of fireworks. Though they share some common characteristics, each type works a little differently.

Firecrackers

Firecrackers are the original fireworks. In their simplest form, firecrackers consists of gunpowder wrapped in paper, with a fuse. Gunpowder consists of 75% potassium nitrate (KNO3), 15% charcoal (carbon) or sugar, and 10% sulfur. The materials will react with each other when enough heat is applied. Lighting the fuse supplies the heat to light a firecracker. The charcoal or sugar is the fuel. Potassium nitrate is the oxidizer, and sulfur moderates the reaction. Carbon (from the charcoal or sugar) plus oxygen (from the air and the potassium nitrate) forms carbon dioxide and energy. Potassium nitrate, sulfur, and carbon react to form nitrogen and carbon dioxide gases and potassium sulfide. The pressure from the expanding nitrogen and carbon dioxide explode the paper wrapper of a firecracker. The loud bang is the pop of the wrapper being blown apart.

Sparklers

A sparkler consists of a chemical mixture that is molded onto a rigid stick or wire. These chemicals often are mixed with water to form a slurry that can be coated on a wire (by dipping) or poured into a tube. Once the mixture dries, you have a sparkler. Aluminum, iron, steel, zinc or magnesium dust or flakes may be used to create the bright, shimmering sparks. An example of a simple sparkler recipe consists of potassium perchlorate and dextrin, mixed with water to coat a stick, then dipped in aluminum flakes. The metal flakes heat up until they are incandescent and shine brightly or, at a high enough temperature, actually burn. A variety of chemicals can be added to create colors. The fuel and oxidizer are proportioned, along with the other chemicals, so that the sparkler burns slowly rather than exploding like a firecracker. Once one end of the sparkler is ignited, it burns progressively to the other end. In theory, the end of the stick or wire is suitable to support it while burning.

Rockets & Aerial Shells

When most people think of 'fireworks' an aerial shell probably comes to mind. These are the fireworks that are shot into the sky to explode. Some modern fireworks are launched using compressed air as a propellent and exploded using an electronic timer, but most aerial shells remain launched and exploded using gunpowder. Gunpowder-based aerial shells essentially function like two-stage rockets. The first stage of an aerial shell is a tube containing gunpowder, that is lit with a fuse much like a large firecracker. The difference is that the gunpowder is used to propel the firework into the air rather than explode the tube. There is a hole at the bottom of the firework so the expanding nitrogen and carbon dioxide gases launch the firework into the sky. The second stage of the aerial shell is a package of gunpowder, more oxidizer, and colorants. The packing of the components determines the shape of the firework.
http://chemistry.about.com/od/howthingswork/a/fireworks.htm