Magic acid

From Wikipedia, the free encyclopedia

Magic acid

Fluorosulfuric acid-antimony pentafluoride 1:1
Identifiers
CAS Number	23854-38-8
3D model (JSmol)	Interactive image
ChemSpider	17339394
ECHA InfoCard	100.041.727
PubChem CID	16211378
Properties
Chemical formula	HSbF6SO3
Molar mass	316.82 g/mol
Appearance	Liquid
Hazards
R-phrases (outdated)	R14 R15/29 R16 R17 R18 R19 R26/27/28 R30 R31 R32 R33 R34
S-phrases (outdated)	S26 S27 S36/37/39 S38 S40 S41 S42 S43 S45
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).

Magic acid (FSO₃H·SbF₅) is a superacid consisting of a mixture, most commonly in a 1:1 molar ratio, of fluorosulfuric acid (HSO₃F) and antimony pentafluoride (SbF₅). This conjugate Brønsted–Lewis superacid system was developed in the 1960s by the George Olah lab at Case Western Reserve University, and has been used to stabilize carbocations and hypercoordinated carbonium ions in liquid media. Magic acid and other superacids are also used to catalyze isomerization of saturated hydrocarbons, and have been shown to protonate even weak bases, including methane, xenon, halogens, and molecular hydrogen.

History

The term "superacid" was first used in 1927 when James Bryant Conant found that perchloric acid could protonate ketones and aldehydes to form salts in nonaqueous solution. The term itself was coined by Gillespie later, after Conant combined sulfuric acid with fluorosulfuric acid, and found the solution to be several million times more acidic than sulfuric acid alone. The magic acid system was developed in the 1960s by George Olah, and was to be used to study stable carbocations. Gillespie also used the acid system to generate electron-deficient inorganic cations. The name originated after a Christmas party in 1966, when a member of the Olah lab placed a paraffin candle into the acid, and found that it dissolved quite rapidly. Examination of the solution with ¹H-NMR showed a tert-butyl cation, suggesting that the paraffin chain that forms the wax had been cleaved, then isomerized, and the atoms were arranged into a different shape to form the ion. The name appeared in a paper published by the Olah lab.

Properties

Structure

Although a 1:1 molar ratio of HSO₃F and SbF₅ best generates carbonium ions, the effects of the system at other molar ratios have also been documented. When the ratio SbF₅:HSO₃F is less than 0.2, the following two equilibria, determined by ¹⁹F NMR spectroscopy, are the most prominent in solution:

(In both of these structures, the sulfur has tetrahedral coordination, not planar. The double bonds between sulfur and oxygen are more properly represented as single bonds, with formal negative charges on the oxygen atoms and a formal plus two charge on the sulfur. The antimony atoms will also have a formal charge of minus one.) 

In the above figure, Equilibrium I accounts for 80% of the NMR data, while Equilibrium II accounts for about 20%. As the ratio of the two compounds increases from 0.4–1.4, new NMR signals appear and increase in intensity with increasing concentrations of SbF₅. The resolution of the signals decreases as well, because of the increasing viscosity of the liquid system.

Strength

All proton-producing acids stronger than 100% sulfuric acid are considered superacids, and are characterized by low values of the Hammett acidity function. For instance, sulfuric acid, H₂SO₄, has a Hammett acidity function, H₀, of −12, perchloric acid, HClO₄, has a Hammett acidity function, of −13, and that of the 1:1 magic acid system, HSO₃F·SbF₅, is −23. Fluoroantimonic acid, the strongest known superacid, can reach up to H₀ = −28.

Uses

Observations of stable carbocations

Magic acid has low nucleophilicity, allowing for increased stability of carbocations in solution. The "classical" trivalent carbocation can be observed in the acid medium, and has been found to be planar and sp²-hybridized. Because the carbon has only six valence electrons, it is highly electron deficient and electrophilic. It is easily described by Lewis dot structures because it contains only two-electron, two-carbon bonds. Many tertiary cycloalkyl cations can also be formed in superacidic solutions. One such example is the 1-methyl-1-cyclopentyl cation, which is formed from both the cyclopentane and cyclohexane precursor. In the case of the cyclohexane, the cyclopentyl cation is formed from isomerization of the secondary carbocation to the tertiary, more stable carbocation. Cyclopropylcarbenium ions, alkenyl cations, and arenium cations have also been observed. 

As use of the Magic acid system became more widespread, however, higher-coordinate carbocations were observed. Penta-coordinate carbocations, also described as nonclassical ions, cannot be depicted using only two-electron, two-center bonds, and require, instead, two-electron, three (or more) center bonding. In these ions, two electrons are delocalized over more than two atoms, rendering these bond centers so electron deficient that they enable saturated alkanes to participate in electrophilic reactions. The discovery of hypercoordinated carbocations fueled the nonclassical ion controversy of the 1950s and 60s. Due to the slow timescale of ¹H-NMR, the rapidly equilibrating positive charges on hydrogen atoms would likely go undetected. However, IR spectroscopy, Raman spectroscopy, and ¹³C NMR have been used to investigate bridged carbocation systems. One controversial cation, the norbornyl cation, has been observed in several media, Magic acid among them.

The bridging methylene carbon atom is pentacoordinated, with three two-electron, two-center bonds, and one two-electron, three-center bond with its remaining sp³ orbital. Quantum mechanical calculations have also shown that the classical model is not an energy minimum.

Reactions with alkanes

Magic acid is capable of protonating alkanes. For instance, methane reacts to form the CH⁺
₅ ion at 140 °C and atmospheric pressure, though some hydrocarbon ions of greater molecular weights are also formed as byproducts. Hydrogen gas is another reaction byproduct.

In the presence of FSO₃D rather than FSO₃H, methane has been shown to interchange hydrogen atoms for deuterium atoms, and HD is released rather than H₂. This is evidence to suggest that in these reactions, methane is indeed a base, and can accept a proton from the acid medium to form CH⁺
₅. This ion is then deprotonated, explaining the hydrogen exchange, or loses a hydrogen molecule to form CH⁺
₃ – the carbonium ion. This species is quite reactive, and can yield several new carbocations, shown below.

Larger alkanes, such as ethane, are also reactive in magic acid, and both exchange hydrogen atoms and condense to form larger carbocations, such as protonated neopentane. This ion is then cloven at higher temperatures, and reacts to release hydrogen gas and forms the t-amyl cation at lower temperatures.

It is on this note that George Olah suggests we no longer take as synonymous the names "alkane" and "paraffin." The word "paraffin" is derived from the Latin "parum affinis", meaning "lacking in affinity." He says, "It is, however, with some nostalgia that we make this recommendation, as ‘inert gases’ at least maintained their ‘nobility’ as their chemical reactivity became apparent, but referring to ‘noble hydrocarbons’ would seem to be inappropriate."

Catalysis with hydroperoxides

Magic acid catalyzes cleavage-rearrangement reactions of tertiary hydroperoxides and tertiary alcohols. The nature of the experiments used to determine the mechanism, namely the fact that they took place in superacid medium, allowed observation of the carbocation intermediates formed. It was determined that the mechanism depends on the amount of magic acid used. Near molar equivalency, only O–O cleavage is observed, but with increasing excess of magic acid, C–O cleavage competes with O–O cleavage. The excess acid likely deactivates the hydrogen peroxide formed in C–O heterolysis.

Magic acid also catalyzes electrophilic hydroxylation of aromatic compounds with hydrogen peroxide, resulting in high-yield preparation of monohydroxylated products. Phenols exist as completely protonated species in superacid solutions, and when produced in the reaction, are then deactivated toward further electrophilic attack. Protonated hydrogen peroxide is the active hydroxylating agent.

Catalysis with ozone

Oxygenation of alkanes can be catalyzed by a magic acid–SO₂ClF solution in the presence of ozone. The mechanism is similar to that of protolysis of alkanes, with an electrophilic insertion into the single σ bonds of the alkane. The hydrocarbon–ozone complex transition state has the form of a penta-coordinated ion.

Alcohols, ketones, and aldehydes are oxygenated by electrophilic insertion as well.

Safety

As with all strong acids, and especially superacids, proper personal protective equipment should be used. In addition to the obligatory gloves and goggles, the use of a faceshield and full-face respirator are also recommended. Predictably, magic acid is highly toxic upon ingestion and inhalation, causes severe skin and eye burns, and is toxic to aquatic life.

Rocket engine nozzle

From Wikipedia, the free encyclopedia

Figure 1: A de Laval nozzle, showing approximate flow velocity increasing from green to red in the direction of flow

 

Nozzle on the first stage of an RSA-3 rocket

 

A rocket engine nozzle is a propelling nozzle (usually of the de Laval type) used in a rocket engine to expand and accelerate the combustion gases produced by burning propellants so that the exhaust gases exit the nozzle at hypersonic velocities. 

Simply: the rocket (pumps and a combustion chamber) generates high pressure, a few hundred atmospheres. The nozzle turns the static high pressure high temperature gas into rapidly moving gas at near-ambient pressure.

History

The de Laval nozzle was originally developed in the 19th century by Gustaf de Laval for use in steam turbines. It was first used in an early rocket engine developed by Robert Goddard, one of the fathers of modern rocketry. It has since been used in almost all rocket engines, including Walter Thiel's implementation, which made possible Germany's V-2 rocket.

Atmospheric use

The optimal size of a rocket engine nozzle to be used within the atmosphere is achieved when the exit pressure equals ambient (atmospheric) pressure, which decreases with altitude. For rockets travelling from the Earth to orbit, a simple nozzle design is only optimal at one altitude, losing efficiency and wasting fuel at other altitudes. 

Just past the throat, the pressure of the gas is higher than ambient pressure and needs to be lowered between the throat and the nozzle exit by expansion. If the pressure of the jet leaving the nozzle exit is still above ambient pressure, then a nozzle is said to be "underexpanded"; if the jet is below ambient pressure, then it is "overexpanded". 

Slight overexpansion causes a slight reduction in efficiency, but otherwise does little harm. However, if the exit pressure is less than approximately 40% that of ambient, then "flow separation" occurs. This can cause jet instabilities that can cause damage to the nozzle or simply cause control difficulties of the vehicle or the engine. 

In some cases it is desirable for reliability and safety reasons to ignite a rocket engine on the ground that will be used all the way to orbit. For optimal liftoff performance, the pressure of the gases exiting nozzle should be at sea-level pressure; however, if a rocket engine is primarily designed for use at high altitudes and is only providing additional thrust to another "first-stage" engine during liftoff in a multi-stage design, then designers will usually opt for an overexpanded nozzle (at sea-level) design, making it more efficient at higher altitudes, where the ambient pressure is lower. This was the technique employed on the Space shuttle's main engines, which spent most of their powered trajectory in near-vacuum, while the shuttle's two solid rocket boosters provided the majority of the liftoff thrust.

Vacuum use

For nozzles that are used in vacuum or at very high altitude, it is impossible to match ambient pressure; rather, nozzles with larger area ratio are usually more efficient. However, a very long nozzle has significant mass, a drawback in and of itself. A length that optimises overall vehicle performance typically has to be found. Additionally, as the temperature of the gas in the nozzle decreases, some components of the exhaust gases (such as water vapour from the combustion process) may condense or even freeze. This is highly undesirable and needs to be avoided. 

Magnetic nozzles have been proposed for some types of propulsion (for example VASIMR), in which the flow of plasma or ions are directed by magnetic fields instead of walls made of solid materials. These can be advantageous, since a magnetic field itself cannot melt, and the plasma temperatures can reach millions of kelvins. However, there are often thermal design challenges presented by the coils themselves, particularly if superconducting coils are used to form the throat and expansion fields.

One-dimensional analysis of gas flow in rocket engine nozzles

Diagram of a de Laval nozzle, showing flow velocity (v) increasing in the direction of flow, with decreases in temperature (t) and pressure (p). The Mach number (M) increases from subsonic, to sonic at the throat, to supersonic.

The analysis of gas flow through de Laval nozzles involves a number of concepts and simplifying assumptions:

• The combustion gas is assumed to be an ideal gas.
• The gas flow is isentropic i.e., at constant entropy, as the result of the assumption of non-viscous fluid, and adiabatic process.
• The gas flow is constant (i.e., steady) during the period of the propellant burn.
• The gas flow is non-turbulent and axisymmetric from gas inlet to exhaust gas exit (i.e., along the nozzle's axis of symmetry)
• The flow behavior is compressible since the fluid is a gas.

As the combustion gas enters the rocket nozzle, it is traveling at subsonic velocities. As the throat constricts, the gas is forced to accelerate until at the nozzle throat, where the cross-sectional area is the least, the linear velocity becomes sonic. From the throat the cross-sectional area then increases, the gas expands and the linear velocity becomes progressively more supersonic. 

The linear velocity of the exiting exhaust gases can be calculated using the following equation 

${\displaystyle v_{e}={\sqrt {\,{\frac {T\,R}{M}}\cdot {\frac {2\;\gamma }{\gamma -1}}\cdot \left[1-\left({\frac {p_{e}}{p}}\right)^{\frac {\gamma -1}{\gamma }}\right]}}}$

where:
${\displaystyle v_{e}}$,	exhaust velocity at nozzle exit (m/s)
${\displaystyle T}$,	absolute temperature of inlet gas (K)
${\displaystyle R}$	= 8314.5 J/kmol·K, universal gas law constant
${\displaystyle M}$,	the gas molecular mass or weight, (kg/kmol)
${\displaystyle \gamma }$	${\displaystyle =c_{p}/c_{v}}$, isentropic expansion factor
${\displaystyle c_{p}}$,	specific heat of the gas at constant pressure
${\displaystyle c_{v}}$,	specific heat of the gas at constant volume
${\displaystyle p_{e}}$,	absolute pressure of exhaust gas at nozzle exit (Pa)
${\displaystyle p}$,	absolute pressure of inlet gas (Pa)

Some typical values of the exhaust gas velocity v_e for rocket engines burning various propellants are:

• 1.7 to 2.9 km/s (3800 to 6500 mi/h) for liquid monopropellants
• 2.9 to 4.5 km/s (6500 to 10100 mi/h) for liquid bipropellants
• 2.1 to 3.2 km/s (4700 to 7200 mi/h) for solid propellants

As a note of interest, v_e is sometimes referred to as the ideal exhaust gas velocity because it based on the assumption that the exhaust gas behaves as an ideal gas.

As an example calculation using the above equation, assume that the propellant combustion gases are: at an absolute pressure entering the nozzle of p = 7.0 MPa and exit the rocket exhaust at an absolute pressure of p_e = 0.1 MPa; at an absolute temperature of T = 3500 K; with an isentropic expansion factor of γ = 1.22 and a molar mass of M = 22 kg/kmol. Using those values in the above equation yields an exhaust velocity v_e = 2802 m/s or 2.80 km/s which is consistent with above typical values.

The technical literature can be very confusing because many authors fail to explain whether they are using the universal gas law constant R which applies to any ideal gas or whether they are using the gas law constant R_s which only applies to a specific individual gas. The relationship between the two constants is R_s = R/M, where R is the universal gas constant, and M is the molar mass of the gas.

Specific impulse

Thrust is the force that moves a rocket through the air or space. Thrust is generated by the propulsion system of the rocket through the application of Newton's third law of motion: "For every action there is an equal and opposite reaction". A gas or working fluid is accelerated out the rear of the rocket engine nozzle, and the rocket is accelerated in the opposite direction. The thrust of a rocket engine nozzle can be defined as:

${\displaystyle {\begin{aligned}F&={\dot {m}}v_{\text{e}}+\left(p_{\text{e}}-p_{\text{o}}\right)A_{e}\\[2pt]&={\dot {m}}\left[v_{\text{e}}+\left({\frac {p_{\text{e}}-p_{\text{o}}}{\dot {m}}}\right)A_{\text{e}}\right],\end{aligned}}}$

and for perfectly expanded nozzles, this reduces to:

${\displaystyle F={\dot {m}}v_{\text{eq}}.}$

The specific impulse ${\displaystyle I_{\text{sp}}}$ is the ratio of the thrust produced to the weight flow of the propellants. It is a measure of the fuel efficiency of a rocket engine. In English Engineering units it can be obtained as

${\displaystyle I_{\text{sp}}={\frac {F}{{\dot {m}}g_{\text{o}}}}={\frac {{\dot {m}}v_{\text{eq}}}{{\dot {m}}g_{\text{o}}}}={\frac {v_{\text{eq}}}{g_{\text{o}}}},}$

where:
${\displaystyle F}$,	gross rocket engine thrust (N)
${\displaystyle {\dot {m}}}$,	mass flow rate of exhaust gas (kg/s)
${\displaystyle v_{\text{e}}}$,	exhaust gas velocity at nozzle exit (m/s)
${\displaystyle p_{\text{e}}}$,	exhaust gas pressure at nozzle exit (Pa)
${\displaystyle p_{\text{o}}}$,	external ambient pressure, or free stream pressure (Pa)
${\displaystyle A_{\text{e}}}$,	cross-sectional area of nozzle exhaust exit (m²)
${\displaystyle v_{\text{eq}}}$,	equivalent (or effective) exhaust gas velocity at nozzle exit (m/s)
${\displaystyle I_{\text{sp}}}$,	specific impulse (s)
${\displaystyle g_{\text{o}}}$,	standard gravitational acceleration at sea level on Earth = 9.807 m/s²

In certain cases, where ${\displaystyle p_{\text{e}}}$ equals ${\displaystyle p_{\text{o}}}$, the formula becomes

${\displaystyle I_{\text{sp}}={\frac {F}{{\dot {m}}\,g_{\text{o}}}}\,=\,{\frac {{\dot {m}}\,v_{\text{e}}}{{\dot {m}}\,g_{\text{o}}}}\,=\,{\frac {v_{\text{e}}}{g_{\text{o}}}}}$

In cases where this may not be so, since for a rocket nozzle ${\displaystyle p_{\text{e}}}$ is proportional to ${\displaystyle {\dot {m}}}$, it is possible to define a constant quantity that is the vacuum ${\displaystyle I_{\text{sp,vac}}}$ for any given engine thus:

${\displaystyle I_{\text{sp,vac}}={\frac {v_{\text{e}}}{g_{\text{o}}}}+{\frac {p_{\text{e}}A_{\text{e}}}{{\dot {m}}g_{\text{o}}}},}$

and hence:

${\displaystyle F=I_{\text{sp,vac}}\,g_{\text{o}}{\dot {m}}-A_{\text{e}}p_{\text{o}},}$

which is simply the vacuum thrust minus the force of the ambient atmospheric pressure acting over the exit plane. 

Essentially then, for rocket nozzles, the ambient pressure acting on the engine cancels except over the exit plane of the rocket engine in a rearward direction, while the exhaust jet generates forward thrust. 

Nozzles can be (top to bottom):

• underexpanded
• ambient
• overexpanded
• grossly overexpanded.

If a nozzle is under- or overexpanded, then loss of efficiency occurs relative to an ideal nozzle. Grossly overexpanded nozzles have improved efficiency relative to an underexpanded nozzle (though are still less efficient than a nozzle with the ideal expansion ratio), however the exhaust jet is unstable.

Aerostatic back-pressure and optimal expansion

As the gas travels down the expansion part of the nozzle, the pressure and temperature decrease, while the speed of the gas increases.

The supersonic nature of the exhaust jet means that the pressure of the exhaust can be significantly different from ambient pressure – the outside air is unable to equalize the pressure upstream due to the very high jet velocity. Therefore, for supersonic nozzles, it is actually possible for the pressure of the gas exiting the nozzle to be significantly below or very greatly above ambient pressure. 

If the exit pressure is too low, then the jet can separate from the nozzle. This is often unstable, and the jet will generally cause large off-axis thrusts and may mechanically damage the nozzle.

This separation generally occurs if the exit pressure drops below roughly 30–45% of ambient, but separation may be delayed to far lower pressures if the nozzle is designed to increase the pressure at the rim, as is achieved with the SSME (1–2 psi at 15 psi ambient).

In addition, as the rocket engine starts up or throttles, the chamber pressure varies, and this generates different levels of efficiency. At low chamber pressures the engine is almost inevitably going to be grossly over-expanded.

Optimal shape

The ratio of the area of the narrowest part of the nozzle to the exit plane area is mainly what determines how efficiently the expansion of the exhaust gases is converted into linear velocity, the exhaust velocity, and therefore the thrust of the rocket engine. The gas properties have an effect as well. 

The shape of the nozzle also modestly affects how efficiently the expansion of the exhaust gases is converted into linear motion. The simplest nozzle shape has a ~15° cone half-angle, which is about 98% efficient. Smaller angles give very slightly higher efficiency, larger angles give lower efficiency.

More complex shapes of revolution are frequently used, such as Bell nozzles or parabolic shapes. These give perhaps 1% higher efficiency than the cone nozzle and can be shorter and lighter. They are widely used on launch vehicles and other rockets where weight is at a premium. They are, of course, harder to fabricate, so are typically more costly. 

There is also a theoretically optimal nozzle shape for maximal exhaust speed. However, a shorter bell shape is typically used, which gives better overall performance due to its much lower weight, shorter length, lower drag losses, and only very marginally lower exhaust speed.

Other design aspects affect the efficiency of a rocket nozzle. The nozzle's throat should have a smooth radius. The internal angle that narrows to the throat also has an effect on the overall efficiency, but this is small. The exit angle of the nozzle needs to be as small as possible (about 12°) in order to minimize the chances of separation problems at low exit pressures.

Advanced designs

A number of more sophisticated designs have been proposed for altitude compensation and other uses. 

Nozzles with an atmospheric boundary include:

• expansion-deflection nozzle,
• plug nozzle,
• aerospike,
• Single Expansion Ramp Nozzle (SERN), a linear expansion nozzle, where the gas pressure transfers work only on one side and which could be described as a single-sided aerospike nozzle.

Each of these allows the supersonic flow to adapt to the ambient pressure by expanding or contracting, thereby changing the exit ratio so that it is at (or near) optimal exit pressure for the corresponding altitude. The plug and aerospike nozzles are very similar in that they are radial in-flow designs but plug nozzles feature a solid centerbody (sometimes truncated) and aerospike nozzles have a "base-bleed" of gases to simulate a solid center-body. ED nozzles are radial out-flow nozzles with the flow deflected by a center pintle.

Controlled flow-separation nozzles include:

• expanding nozzle,
• bell nozzles with a removable insert,
• Stepped nozzles, or dual-bell nozzles.

These are generally very similar to bell nozzles but include an insert or mechanism by which the exit area ratio can be increased as ambient pressure is reduced. 

Dual-mode nozzles include:

• dual-expander nozzle,
• dual-throat nozzle.

These have either two throats or two thrust chambers (with corresponding throats). The central throat is of a standard design and is surrounded by an annular throat, which exhausts gases from the same (dual-throat) or a separate (dual-expander) thrust chamber. Both throats would, in either case, discharge into a bell nozzle. At higher altitudes, where the ambient pressure is lower, the central nozzle would be shut off, reducing the throat area and thereby increasing the nozzle area ratio. These designs require additional complexity, but an advantage of having two thrust chambers is that they can be configured to burn different propellants or different fuel mixture ratios. Similarly, Aerojet has also designed a nozzle called the "Thrust Augmented Nozzle", which injects propellant and oxidiser directly into the nozzle section for combustion, allowing larger area ratio nozzles to be used deeper in an atmosphere than they would without augmentation due to effects of flow separation. They would again allow multiple propellants to be used (such as RP-1), further increasing thrust.

Liquid injection thrust vectoring nozzles are another advanced design that allow pitch and yaw control from un-gimbaled nozzles. India's PSLV calls its design "Secondary Injection Thrust Vector Control System"; strontium perchlorate is injected through various fluid paths in the nozzle to achieve the desired control. Some ICBMs and boosters, such as the Titan IIIC and Minuteman II, use similar designs.