evade it, as the embargo also did great harm to Spanish economic interests, even to the extent that for a time a famine threatened in Spanish Naples when the Dutch carried grain trade was cut off Realizing that the local authorities often sabotaged the embargo, the Spanish crown built up an elaborate enforcement apparatus, the Almirantazgo de los paises septentrionales Admiralty of the northern countries in to make it more effective Part of the new system was a network of inspectors in neutral ports who inspected neutral shipping for goods with a Dutch connection and supplied certificates that protected neutral shippers against confiscation in Spanish ports The English and Hanseatics were only too happy to comply, and so contributed to the effectiveness of the embargo The embargo grew to an effective direct and indirect impediment for Dutch trade, as not only the direct trade between the Amsterdam Entrepôt and the lands of the Spanish empire was affected, but also the parts of Dutch trade that indirectly depended on it Baltic grain and naval stores destined for Spain were now provided by others, depressing the Dutch trade with the Baltic area the carrying trade between Spain and Italy now shifted to English shipping etc The embargo was a double edged sword, however, as some Spanish and Portuguese export activities likewise collapsed as a consequence of the embargo such as the Valencian and Portuguese salt exports Spain was also able to physically close off these inland waterways after for Dutch river traffic The Dutch were thus also deprived of their important transit trade with the neutral Prince Bishopric of Liège then not a part of the Southern Netherlands and the German hinterland in these years Dutch butter and cheese prices collapsed as a result of this blockade and rose steeply in the affected import areas , as did wine and herring prices the Dutch monopolised the French wine trade at the time , but the steep price rises in the Spanish Netherlands, sometimes accompanied by food shortages, led to an eventual relaxation of this embargo It was eventually abandoned, because it deprived the Brussels authorities from important revenues from custom duties The economic warfare measures of Spain were effective in the sense that they depressed economic activity in the Netherlands, thereby also depressing Dutch fiscal resources to finance the war effort, but also by structurally altering European trade relations, at least until the end of the war, after which they reverted in favour of the Dutch Neutrals benefited, but both the Dutch and the Spanish areas suffered economically, though not uniformly, as some industrial areas benefited from the artificial

restriction of trade, which had a protectionist effect The new draperies textile industry in Holland permanently lost terrain to its competitors in Flanders and England, though this was compensated for by a shift to more expensive high quality woollens Nevertheless, the economic pressure and the slump of trade and industry it caused was not sufficient to bring the Republic to its knees There were a number of reasons for this The chartered companies, both VOC and WIC, provided employment on a large enough scale to compensate for the slump in other forms of trade and their trade brought great revenues Supplying the armies, both in the Netherlands and in Germany, proved a boon for the agricultural areas in the Dutch inland provinces The fiscal situation of the Dutch government also improved after the death of Maurice in He had been too successful in gathering all reins of government in his own hands after his coup in He completely dominated Dutch politics and diplomacy in his first years afterwards, even monopolising the abortive peace talks before the expiration of the Truce Likewise the political Counter Remonstrants were temporarily in total control, but the downside of all this was that his government was overextended, with too few people doing the heavy lifting on the local level, which was essential to make the government machine run smoothly in the highly decentralised Dutch polity Holland's conventional role as leader of the political process was temporarily vacated, as Holland as a power center was eliminated Maurice had to do everything by himself with his small band of aristocratic managers in the States General This situation deteriorated even more, when he had to spend long periods in the field as commander in chief, during which he was unable to personally direct affairs in The Hague His health soon deteriorated, also detracting from his efficacy as a political and military leader The regime, depending on Maurice's personal qualities as a virtual dictator, therefore came under unbearable strain Not surprisingly, in the period up to his death the strategic and military position of the Republic deteriorated It had to increase the standing army to , men in , just to hold the defensive ring of fortresses, while Spain increased the Army of Flanders to , men at the same time This put a great strain on the Republic's finances at a time when tax rates were already dangerously high Yet at the same time the Republic had no other option than to sustain the imploding German Protestant forces financially For that reason the Dutch paid for the army of Count Ernst von Mansfeld that was cowering against the Dutch border in East Friesland after its defeats against the Spanish and Imperial forces it was hoped that in this way a complete encirclement of the Republic could be avoided For a while the Republic pinned its hope on Christian the Younger of Brunswick However, his Dutch financed army was crushed at Stadtlohn, near the Dutch border by the forces of the Catholic League under Tilly in August This setback necessitated a reinforcement of the Dutch IJssel line Spinola, however, failed to take advantage of the new situation, lulled into complacency by Maurice's unceasing peace feelers He was back in , however, besieging Breda, and Dutch morale slumped, despite the diplomatic success of the Treaty of Compiègne with Louis XIII of France, in which the latter agreed to support the Dutch military effort with an annual subsidy of a million guilders % of the Dutch war budget Maurice died, aged , in April , and was succeeded as Prince of Orange and captain general of the Union by his half brother Frederick Henry, Prince of Orange It took several months, however, to obtain his appointment as stadtholder of Holland and Zeeland, as it took time to agree on the terms of his commission This deprived the regime of leadership in a crucial time During this time the moderate Calvinist regents staged a return in Holland at the expense of the radical Counter Remonstrants This was an important development, as Frederick Henry, could not lean exclusively on the latter faction, but instead took a position above the parties , playing off the two factions against one another A side effect of this was that more normal political relations returned to the Republic, with Holland returning to its central political position Also, the persecution of the Remonstrants now abated with the Prince's connivance, and with this renewed climate of tolerance, political stability in the Republic also improved This improvement in internal affairs helped the Republic overcome the difficult years of the sharpest economic warfare phase During the lull in the military pressure by Spain after the fall of Breda in the Republic was able to steadily increase its standing army, owing to its improved financial situation This enabled the new stadtholder of Friesland and Groningen, Ernst Casimir, to recapture Oldenzaal, forcing the Spanish troops to evacuate Overijssel Diplomatically, the situation improved once England entered the war in as an ally Frederick Henry cleared the Spaniards from eastern Gelderland in after recapturing Grol The Dutch victory in the Battle in the Bay of Matanzas in , in which a Spanish treasure fleet was captured by Piet Pieterszoon Hein, contributed even more to the improving fiscal situation, at the same time depriving Spain of much needed money However, the greatest contribution to the relative improvement of the Dutch position in was made by the fact that Spain overextended itself again, when it participated in the War of the Mantuan Succession This caused such a depletion of Spanish troops and financial resources in the theatre of war in the Netherlands, that the Republic for the time being achieved a strategic superiority the Army of Flanders declined to , men while the States Army reached , in The Republic sallies forth – edit Meanwhile, the Imperial forces had surged in Germany after the initial setback from the intervention of Christian IV of Denmark in the war in Both the Danes and Mansfelt were defeated in and the Catholic League occupied the northern German lands that had hitherto acted as a buffer zone for the Republic For a while an invasion of the eastern part of the Republic seemed imminent in However, the relative might of Spain, the main player up to now in the German civil war, was ebbing fast By April the States Army counted , soldiers, half as much again as the Army of Flanders at that point in time This allowed Frederick Henry to raise a mobile army of , the other troops were used in the fixed garrisons of the Republic and invest 's Hertogenbosch During the siege of this strategic fortress city the imperialist and Spanish allies launched a diversionary attack from Germany's IJssel line After crossing this river, they invaded the Dutch heartland, getting as far as the city of Amersfoort, which promptly surrendered The States General, however, mobilised civic militias and scrounged garrison troops from fortresses all around the country, assembling an army that at the height of the emergency numbered no less than , troops This enabled Frederick Henry to maintain his siege of 's Hertogenbosch When Dutch troops surprised the Spanish fortress of Wesel, which acted as the principal Spanish supply base, this forced the invaders to retreat to the IJssel 's Hertogenbosch surrendered in September to Frederick Henry Frederick Henry and Ernst Casimir at the siege of 'sHertogenbosch by Pauwels van Hillegaert The loss of Wesel and 's Hertogenbosch a city that had been fortified according to the most modern standards, often incorporating Dutch innovations in fortification , in short succession, caused a sensation in Europe It demonstrated that the Dutch, for the moment, enjoyed strategic superiority 's Hertogenbosch was the linchpin of the ring of Spanish fortifications in Brabant its loss left a gaping hole in the Spanish front Thoroughly shaken, Philip IV now overruled Olivares and offered an unconditional truce The States General refused to consider this offer, until the Imperial forces had left Dutch territory Only after this had been accomplished they remitted the Spanish offer to the States of the provinces for consideration The popular debate that followed split the provinces Friesland, Groningen and Zeeland, predictably, rejected the proposal Frederick Henry appears to have favoured it personally, but he was hampered by the political divisions in the province of Holland where radical Counter Remonstrants and moderates were unable to agree The Counter Remonstrants urged in guarded terms a final eradication of Remonstrant tendencies in the Republic thus establishing internal unity before a truce could even be considered The radical Calvinist preachers urged a liberation of more of the Spanish Netherlands Shareholders in the WIC dreaded the prospect of a truce in the Americas, which would thwart the plans of that company to stage an invasion of Portuguese Brazil The peace party and the war party in the States of Holland therefore perfectly balanced each other and deadlock ensued Nothing was decided during and To break the deadlock in the States of Holland, Frederick Henry planned a sensational offensive in He intended to invade Flanders, and make a deep thrust toward Dunkirk, like his brother had done in His expedition was even larger He embarked , men and field guns on , rivercaft for his amphibious descent on IJzendijke From there he penetrated to the Bruges Ghent canal that the Brussels government had dug to circumvent the Dutch blockade of the coastal waters Unfortunately, at this stage a sizeable Spanish force appeared in his rear and this caused a row with panicky deputies in the field that, as usual, were micro managing the campaign for the States General The civilians prevailed, and a very angry Frederick Henry had to order an ignominious retreat of the Dutch invading force Finally, in , Frederick Henry was allowed to deliver his death blow The initial move in his offensive was to have a reluctant States General publish over the objections of the radical Calvinists a proclamation promising that the free exercise of the Catholic religion would be guaranteed in places that the Dutch army would conquer that year The inhabitants of the Southern Netherlands were invited to throw off the yoke of the Spaniards This piece of propaganda would prove to be very effective Frederick Henry now invaded the Meuse valley with , troops He took Venlo, Roermond and Sittard in short order As promised, the Catholic churches and clergy were left unmolested Then, on June, he laid siege to Maastricht A desperate effort of Spanish and Imperialist forces to relieve the city failed and on August , Frederick Henry sprang his mines, breaching the walls of the city It capitulated three days later Here also, the Catholic religion was allowed to remain The infanta Isabella was now forced to convene the southern States General for the first time since her inauguration in They met in September as it turned out for the last time under Spanish rule Most southern provinces advocated immediate peace talks with the Republic so as to preserve the integrity of the South and the free exercise of the Catholic religion A southern States General delegation met the northern States General, represented by its deputies in the field in Maastricht The southern delegates offered to negotiate on the strength of the authorisation given in by Philip IV However, Philip and Olivares secretly cancelled this authorisation, as they considered the initiative of the southern States General an usurpation of royal power They never intended to honour any agreement that might ensue On the Dutch side, there was the usual disunity Frederick Henry hoped to achieve a quick result, but Friesland, Groningen and Zeeland opposed the talks outright, while divided Holland dithered Eventually, those four provinces authorised talks with only the southern provinces, leaving Spain out Evidently, such an approach would make the resulting agreement worthless, as only Spain possessed any troops The peace party in the Republic finally brought about meaningful negotiations in December , when valuable time had already been lost, enabling Spain to send reinforcements Both sides presented demands that were unreconcilable at first, but after much palaver the southern demands were reduced to the evacuation of Portuguese Brazil which had been invaded by the WIC in by the Dutch In return, they offered Breda and an indemnity for the WIC for giving up Brazil The Dutch over the opposition of the war party that considered the demands too lenient reduced its demands to Breda, Geldern, and the Meierij area around 's Hertogenbosch, in addition to tariff concessions in the South Furthermore, as they realised that Spain would never concede Brazil, they proposed to limit the peace to Europe, continuing the war overseas By June the talks were on the verge of collapse A shift in Dutch politics now ensued, which would prove fateful for the Republic Frederick Henry, sensing that the talks were going nowhere, proposed to put an ultimatum to the other side to accept the Dutch demands However, he now lost the support of the peace party in Holland, led by Amsterdam These regents wanted to offer further concessions to gain peace The peace party gained the upper hand in Holland, for the first time since standing up to the stadtholder and the Counter Remonstrants Frederick Henry, however, managed to gain the support of the majority of the other provinces and those voted on December overruling Holland and Overijssel to break off the talks Franco Dutch Alliance – edit While the peace negotiations had been dragging on, events elsewhere in Europe of course had not stood still While Spain was busy fighting the Mantuan war, the Swedes had intervened in the Thirty Years' War in Germany under Gustavus Adolphus in , supported by French and Dutch subsidies The Swedes used the new Dutch infantry tactics enhanced with improved cavalry tactics with much more success against the Imperialist forces than the German Protestants had done and so gained a number of important successes, turning the tide in the war However, once Spain had her hands free again after the end of the war in Italy in , she was able to bring her forces in the northern theatre of war up to strength again The Cardinal Infante brought a strong army up, by way of the Spanish Road, and at the Battle of Nördlingen this army, combined with Imperialist forces, using the traditional Spanish tercio tactics, decisively defeated the Swedes He then marched immediately on Brussels, where he succeeded the old Infanta Isabella who had died in December Spain's strength in the Southern Netherlands was now appreciably enhanced citation needed The naval battle against the Spanish near Dunkerque, February The Dutch, now no longer any prospect of peace with Spain, and faced with a resurgent Spanish force, decided to take the French overtures for an offensive alliance against Spain more seriously This change in strategic policy was accompanied by a political sea change within the Republic The peace party around Amsterdam objected to the clause in the proposed treaty with France that bound the Republic's hands by prohibiting the conclusion of a separate peace with Spain This would shackle the Republic to French policies and so constrain its independence The resistance to the French alliance by the moderate regents caused a rupture in the relations with the stadtholder Henceforth Frederick Henry would be much more closely aligned with the radical Counter Remonstrants who supported the alliance This political shift promoted the concentration of power and influence in the Republic in the hands of a small group of the stadtholder's favourites These were the members of the several secrete besognes secret committees to which the States General more and more entrusted the conduct of diplomatic and military affairs Unfortunately, this shift to secret policy making by a few trusted courtiers also opened the way for foreign diplomats to influence policy making with bribes Some members of the inner circle performed prodigies of corruption For instance, Cornelis Musch, the griffier clerk of the States General received , livres for his services in pushing the French treaty through from Cardinal Richelieu, while the pliable Grand Pensionary Jacob Cats who had succeeded Adriaan Pauw, the leader of the opposition against the alliance , received , livres The Treaty of Alliance that was signed in Paris in February , committed the Republic to invade the Spanish Netherlands simultaneously with France in The treaty previewed a partitioning of that country between the two invaders If the inhabitants would rise against Spain, the Southern Netherlands would be afforded independence on the model of the Cantons of Switzerland, however with the Flemish seacoast, Namur and Thionville annexed by France, and Breda, Geldern and Hulst going to the Republic If the inhabitants resisted, the country would be partitioned outright, with the Francophone provinces and western Flanders going to France, and the remainder to the Republic The latter partitioning opened the prospect that Antwerp would be re united with the Republic, and the Scheldt reopened for trade on that city, something Amsterdam was very much opposed to The treaty also provided that the Catholic religion would be preserved in its entirety in the provinces to be apportioned to the Republic This provision was understandable from the French point of view, as the French government had recently suppressed the Huguenots in their strongpoint of La Rochelle with support of the Republic , and generally was reducing Protestant privileges It enraged the radical Calvinists in the Republic, however The treaty was not popular in the Republic for those reasons Siege of the Schenkenschans by Gerrit van Santen Dividing up the Spanish Netherlands proved more difficult than foreseen, however Olivares had drawn up a strategy for this two front war, that proved very effective Spain went on the defensive against the French forces that invaded in May and successfully held them at bay The Cardinal Infante brought his full offensive forces to bear on the Dutch, however, in hopes of knocking them out of the war in an early stage, after which France would soon come to terms herself, it was hoped The Army of Flanders now again numbered , men, at least at parity with the Dutch forces Once the force of the double invasion by France and the Republic had been broken, these troops emerged from their fortresses and attacked the recently conquered Dutch areas in a pincer movement In July Spanish troops from Geldern captured the strategically essential fortress of the Schenkenschans This was situated on an island in the Rhine near Cleves and dominated the back door into the Dutch heartland along the north bank of the river Rhine Cleves itself was soon captured by a combined Imperialist Spanish force and Spanish forces overran the Meierij The Republic could not let the capture of the Schenkenschans stand Frederick Henry therefore concentrated a huge force to besiege the fortress even during the winter months of Spain held tenaciously on to the fortress and its strategic corridor through Cleves She hoped that the pressure on this strategic point, and the threat of unhindered invasion of Gelderland and Utrecht, would force the Republic to give in The planned Spanish invasion never materialised, however, as the stadtholder forced the surrender of the Spanish garrison in Schenkenschans in April This was a severe blow for Spain The next year, thanks to the fact that the Cardinal Infante shifted the focus of his campaign to the French border in that year, Frederick Henry managed to recapture Breda with a relatively small force, at the successful fourth Siege of Breda, July– October This operation, which engaged his forces for a full season, was to be his last success for a long time, as the peace party in the Republic, over his objections, managed to cut war expenditure and shrink the size of the Dutch army These economies were pushed through despite the fact that the economic situation in the Republic had improved appreciably in the s, following the economic slump of the s caused by the Spanish embargoes The Spanish river blockade had ended in The end of the Polish–Swedish War in ended the disruption of Dutch Baltic trade The outbreak of the Franco Spanish War closed the alternate trade route through France for Flemish exports, forcing the South to pay the heavy Dutch wartime tariffs Increased German demand for foodstuffs and military supplies as a consequence of military developments in that country, contributed to the economic boom in the Republic, as did successes of the VOC in the Indies and the WIC in the Americas where the WIC had gained a foothold in Portuguese Brazil after its invasion, and now conducted a thriving sugar trade The boom generated much income and savings, but there were few investment possibilities in trade, due to the persisting Spanish trade embargoes As a consequence, the Republic experienced a number of speculative bubbles in housing, land the lakes in North Holland were drained during this period and, notoriously, tulips Despite this economic upswing, which translated into increased fiscal revenues, the Dutch regents showed little enthusiasm for maintaining the high level of military expenditures of the middle s The échec of the Battle of Kallo of June


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jeanie-marie-sullivan jean-jennings jeanna-fine jeannie-pepper jenna-jameson jenna-jane jenna-presley jenna-wells jennifer-haussmann jennifer-janes jennifer-jordan jennifer-morante jennifer-noxt jennifer-stewart jennifer-welles jennifer-west jenny jenny-feeling jenny-fields jenny-wings jersey-jaxin jesie-st-james jesse-capelli jessica-bangkok jessica-bogart jessica-darlin jessica-fiorentino jessica-gabriel jessica-laine jessica-may jessica-road jessica-wylde jessi-foster jill-ferari jill-kelly joana-redgrave joan-devlon joanna-storm joanna-sweet jody-maxwell joelle-lequement joelle-petinot johnni-black jordana-james jordan-green jordan-nevaeh jordan-star josephine-carrington joslyn-james julia-chanel julia-dal-fuoco juliana-grandi julia-paes julia-parton julia-perrin julia-swen julia-thomas julie-meadows julie-rage julie-simone juliet-anderson juliet-graham juliette-carelton kacey-jordan kagney-linn-karter kaitlyn-ashley kalena-rios kami-andrews kamila-smith kandee-licks kandi-barbour 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lise-pinson little-oral-annie liza-dwyer liza-harper lizzy-borden logan-labrent lois-ayres lola-cait long-jean-silver loni-bunny loni-sanders loona-luxx lorelei-lee lorelei-rand lorena-sanchez lori-alexia lori-blue lorrie-lovett luci-diamond lucie-doll lucie-theodorova lucy-van-dam lydia-baum lynn-franciss lynn-lemay lynn-ray lynn-stevens lynx-canon lysa-thatcher madelina-ray madison-parker magdalena-lynn maggie-randall mai-lin mandi-wine mandy-bright mandy-malone mandy-may mandy-mistery mandy-starr marcia-minor maren margit-ojetz margitta-hofer margo-stevens margot-mahler mariah-cherry marianne-aubert maria-tortuga marie-anne marie-christine-chireix marie-christine-veroda marie-claude-moreau marie-dominique-cabannes marie-france-morel marie-luise-lusewitz marie-sharp marilyn-chambers marilyne-leroy marilyn-gee marilyn-jess marilyn-martyn marilyn-star marina-hedman marion-webb marita-ekberg marita-kemper marlena marlene-willoughby marry-queen martine-grimaud martine-schultz maryanne-fisher mary-hubay mary-ramunno mary-stuart mascha-mouton maud-kennedy mauvais-denoir maxine-tyler maya-black maya-france megan-leigh megan-martinez megan-reece mei-ling melanie-hotlips melanie-scott melba-cruz melinda-russell melissa-bonsardo melissa-del-prado melissa-golden melissa-martinez melissa-melendez melissa-monet mercedes-dragon mercedes-lynn merle-michaels mesha-lynn mia-beck mia-lina mia-smiles michele-raven michelle-aston michelle-ferrari michelle-greco michelle-maren michelle-maylene michelle-monroe micki-lynn mika-barthel mika-tan mikki-taylor mimi-morgan mindy-rae ming-toy miranda-stevens miss-bunny miss-meadow miss-pomodoro missy missy-graham missy-stone missy-vega misti-jane mistress-candice misty-anderson misty-dawn misty-rain misty-regan mona-lisa mona-page moni monica-baal monica-swinn monika-peta monika-sandmayr monika-unco monique-bruno monique-cardin monique-charell monique-demoan monique-gabrielle monique-la-belle morgan-fairlane morrigan-hel moxxie-maddron mulani-rivera mysti-may nadege-arnaud nadia-styles nadine-bronx nadine-proutnal nadine-roussial nadi-phuket nanci-suiter nancy-hoffman nancy-vee natacha-delyro natalia-wood natalli-diangelo natascha-throat natasha-skyler naudia-nyce nessa-devil nessy-grant nesty nicki-hunter nicky-reed nicole-berg nicole-bernard nicole-black nicole-grey nicole-london nicole-parks nicole-scott nicole-taylor nicolette-fauludi nicole-west nika-blond nika-mamic niki-cole nikita-love nikita-rush nikki-charm nikki-grand nikki-king nikki-knight nikki-randall nikki-rhodes nikki-santana nikki-steele nikki-wilde niko nina-cherry nina-deponca nina-hartley nina-preta oana-efria obaya-roberts olesja-derevko olga-cabaeva olga-conti olga-pechova olga-petrova olivia-alize olivia-del-rio olivia-flores olivia-la-roche olivia-outre ophelia-tozzi orchidea-keresztes orsolya-blonde paige-turner paisley-hunter pamela-bocchi pamela-jennings pamela-mann pamela-stanford pamela-stealt pandora paola-albini pascale-vital pat-manning pat-rhea patricia-dale patricia-diamond patricia-kennedy patricia-rhomberg patrizia-predan patti-cakes patti-petite paula-brasile paula-harlow paula-morton paula-price paula-winters pauline-teutscher penelope-pumpkins penelope-valentin petra-hermanova petra-lamas peyton-lafferty phaedra-grant pia-snow piper-fawn pipi-anderson porsche-lynn porsha-carrera precious-silver priscillia-lenn purple-passion queeny-love rachel-ashley rachel-love rachel-luv rachel-roxxx rachel-ryan rachel-ryder racquel-darrian rane-revere raven reagan-maddux rebecca-bardoux regan-anthony regine-bardot regula-mertens reina-leone reka-gabor renae-cruz renee-foxx renee-lovins renee-morgan renee-perez renee-summers renee-tiffany rhonda-jo-petty rikki-blake riley-ray rio-mariah rita-ricardo roberta-gemma roberta-pedon robin-byrd robin-cannes robin-everett robin-sane rochell-starr rosa-lee-kimball rosemarie roxanne-blaze roxanne-hall roxanne-rollan ruby-richards sabina-k sabre sabrina-chimaera sabrina-dawn sabrina-jade sabrina-johnson sabrina-love-cox sabrina-mastrolorenzi sabrina-rose sabrina-scott sabrina-summers sacha-davril sahara sahara-sands sai-tai-tiger samantha-fox samantha-ryan samantha-sterlyng samantha-strong samueline-de-la-rosa sandra-cardinale sandra-de-marco sandra-kalermen sandra-russo sandy-lee sandy-pinney sandy-reed sandy-samuel sandy-style sandy-summers sara-brandy-canyon sara-faye sarah-bernard sarah-cabrera sarah-hevyn sarah-mills sarah-shine sara-sloane sasha sasha-hollander sasha-ligaya sasha-rose satine-phoenix satin-summer savannah-stern savanna-jane scarlet-scarleau scarlet-windsor seka selena serena serena-south severine-amoux shana-evans shanna-mccullough shannon-kelly shannon-rush shantell-day sharon-da-vale sharon-kane sharon-mitchell shaun-michelle shawna-sexton shawnee-cates shay-hendrix shayne-ryder sheena-horne sheer-delight shelby-star shelby-stevens shelly-berlin shelly-lyons sheri-st-clair sheyla-cats shonna-lynn shyla-foxxx shy-love sierra-sinn sierra-skye sigrun-theil silver-starr silvia-bella silvia-saint silvie-de-lux silvy-taylor simone-west sindee-coxx sindy-lange sindy-shy siobhan-hunter skylar-knight skylar-price skyler-dupree smokie-flame smoking-mary-jane solange-shannon sonya-summers sophia-santi sophie-call sophie-duflot sophie-evans sophie-guers stacey-donovan stacy-lords stacy-moran stacy-nichols stacy-silver stacy-thorn starla-fox starr-wood stefania-bruni stella-virgin stephanie-duvalle stephanie-rage stephanie-renee stevie-taylor summer-knight summer-rose sunny-day sunset-thomas sunshine-seiber susan-hart susanne-brend susan-nero susi-hotkiss suzanne-mcbain suzan-nielsen suzie-bartlett suzie-carina suzi-sparks sweet-nice sweety-pie sybille-rossani sylvia-benedict sylvia-bourdon sylvia-brand sylvia-engelmann syreeta-taylor syren-de-mer syvette szabina-black szilvia-lauren tai-ellis taija-rae taisa-banx talia-james tamara-lee tamara-longley tamara-n-joy tamara-west tami-white tammy tammy-lee tammy-reynolds tania-lorenzo tantala-ray tanya-danielle tanya-fox tanya-foxx tanya-lawson tanya-valis tara-aire tasha-voux tatjana-belousova tatjana-skomorokhova tawnee-lee tawny-pearl tayla-rox taylor-wane teddi-austin teddi-barrett tera-bond tera-heart tera-joy teresa-may teresa-orlowski teri-diver teri-weigel terri-dolan terri-hall tess-ferre tess-newheart thais-vieira tia-cherry tianna tiara tiffany-blake tiffany-clark tiffany-duponte tiffany-rayne tiffany-rousso tiffany-storm tiffany-towers tiffany-tyler tiger-lily tigr timea-vagvoelgyi tina-blair tina-burner tina-evil tina-gabriel tina-loren tina-marie tina-russell tish-ambrose tommi-rose tonisha-mills topsy-curvey tori-secrets tori-sinclair tori-welles tracey-adams traci-lords traci-topps traci-winn tracy-duzit tracy-love tracy-williams tricia-devereaux tricia-yen trinity-loren trisha-rey trista-post trixie-tyler ultramax ursula-gaussmann ursula-moore uschi-karnat valentina valerie-leveau valery-hilton vanessa-chase vanessa-del-rio vanessa-michaels vanessa-ozdanic vanilla-deville velvet-summers veri-knotty veronica-dol veronica-hart veronica-hill veronica-rayne veronica-sage veronika-vanoza via-paxton vicky-lindsay vicky-vicci victoria-evans victoria-gold victoria-knight victoria-luna victoria-paris victoria-slick victoria-zdrok viper virginie-caprice vivian-valentine vivien-martines wendi-white wendy-divine whitney-banks whitney-fears whitney-wonders wonder-tracey wow-nikki xanthia-berstein yasmine-fitzgerald yelena-shieffer yvonne-green zara-whites zsanett-egerhazi zuzie-boobies

Monarchs The return of Columbus to Spain Seven months before the treaty of Alcaçovas, King John II of Aragon died, and his son Ferdinand II of Aragon, married to the Queen of Castile, Isabella, inherited the thrones of the Crown of Aragon The two became known as the Catholic Monarchs, with their marriage a personal union that created a relationship between the Crown of Aragon and Castile, each with their own administrations, but ruled jointly by the two monarchs After a war of years, the Granada War, in , the Catholic Monarchs drove out the last Moorish king of Granada After their victory, the Catholic Monarchs negotiated with Christopher Columbus, a Genoese sailor attempting to reach Cipangu by sailing west Castile was already engaged in a race of exploration with Portugal to reach the Far East by sea when Columbus made his bold proposal to Isabella In the Capitulations of Santa Fe, dated on April , Christopher Columbus obtained from the Catholic Monarchs his appointment as viceroy and governor in the lands already discovered and that of he might discover thenceforth thereby, it was the first document to establish an administrative organization in the Indies Columbus' discoveries inaugurated the Spanish colonization of the Americas Spain's claim to these lands was solidified by the Inter caetera papal bull dated May , and Dudum siquidem on September , which vested the sovereignty of the territories discovered and to be discovered Since the Portuguese wanted to keep the line of demarcation of Alcaçovas running east and west along a latitude south of Cape Bojador, a compromise was worked out which was incorporated in the Treaty of Tordesillas dated on June , in which the globe was split into two hemispheres dividing Spanish and Portuguese claims These actions gave Spain exclusive rights to establish colonies in all of the New World from north to south except Brazil , as well as the easternmost parts of Asia The treaty of Tordesillas was confirmed by Pope Julius II in the bull Ea quae pro bono pacis on January Spain's expansion and colonization was driven by economic influences, a yearning to improve national prestige, and a desire to spread Catholicism into the New World On the other hand, the treaty of Tordesillas and the treaty of Cintra September established the limits of the Kingdom of Fez for Portugal, and outside of these limits the Castilian expansion was allowed, beginning with the conquest of Melilla in Struggles for Italy edit See also Italian Wars The death of French general Gaston de Foix at the Battle of Ravenna The Catholic Monarchs had developed a strategy of marriages for their children in order to isolate their long time enemy France The Spanish princes married the heirs of Portugal, England and the House of Habsburg Following the same strategy, the Catholic Monarchs decided to support the Catalan Aragonese house of Naples against Charles VIII of France in the Italian Wars from As King of Aragon, Ferdinand had been involved in the struggle against France and Venice for control of Italy these conflicts became the center of Ferdinand's foreign policy as king In these battles, which established the supremacy of the Spanish Tercios in European battlefields, the forces of the kings of Spain acquired a reputation for invincibility that would last until the mid th century After the death of Queen Isabella, Ferdinand, as Spain's sole monarch, adopted a more aggressive policy than he had as Isabella's husband, enlarging Spain's sphere of influence in Italy and against France Ferdinand's first deployment of Spanish forces came in the War of the League of Cambrai against Venice, where the Spanish soldiers distinguished themselves on the field alongside their French allies at the Battle of Agnadello Only a year later, Ferdinand became part of the Holy League against France, seeing a chance at taking both Milan — to which he held a dynastic claim – and Navarre This war was less of a success than the war against Venice, and in , France agreed to a truce that left Milan in its control and recognized Spanish control of Upper Navarre Papal Bulls and the Indies edit Upon the death of Ferdinand the Catholic, the lordship of the Spanish Indies became Kingdoms of the Indies The Papal Bull Inter caetera of by Alexander VI, a Valencian known as Rodrigo Borgia prior to his election as pope, vested government and jurisdiction of newly found lands in the kings of Castile and León and their successors According to the Concord of Segovia of , Ferdinand was mentioned in the bulls as king of Castile and upon his death the title of the Indies was to be incorporated into the Crown of Castile The territories were incorporated by the Catholic Monarchs as jointly held assets In the Treaty of Villafáfila king Ferdinand the Catholic renounced not only the government of Castile in favour of his son in law Philip I of Castile but also the lordship of the Indies, withholding a half of the income of the kingdoms of the Indies Joanna of Castile and Philip immediately added to their titles the kingdoms of Indies, Islands and Mainland of the Ocean Sea But the Treaty of Villafáfila did not hold for long because of the death of Philip Ferdinand returned as regent of Castile and as lord the Indies According to the domain granted by Papal bulls and the wills of queen Isabella of Castile in and king Ferdinand of Aragon in , such property become definitely a property of the Crown of Castile This arrangement was ratified by successive monarchs, beginning with Charles I in in a decree that spelt out the juridical status of the new overseas territories The lordship of the discovery territories conveyed by papal bulls was private as public to kings of Castile and León The political condition of the Indias were to transform from Lordship of the Catholic monarchs to Kingdoms for the heirs of Castile Although the Alexandrine Bulls gave full, free and omnipotent power to Catholic Monarchs, they did not rule them as a private property but as a public property through the public bodies and authorities from Castile, and when those territories were incorporated into the Crown of Castile the royal power was subject to the laws of Castile First settlements in the Americas and Crown control edit See also Voyages of Christopher Columbus and Treaty of Tordesillas The Crown of Castile's Capitulations of Santa Fe granted expansive power to Christopher Columbus, including exploration, settlement, political power, and revenues, with sovereignty reserved to the Crown of Castile The first voyage established sovereignty for the crown and the crown acted on the assumption that Columbus's grandiose assessment of what he found was true, so that Spain negotiated the Treaty of Tordesillas with Portugal to protect their territory on the Spanish side of the line The crown fairly quickly reassessed its relationship to Columbus and moved to assert more direct crown control over the territory and extinguish his privileges With that lesson learned, the crown was far more prudent in the specifying the terms of exploration, conquest, and settlement in new areas The pattern in the Caribbean that played out over the larger Spanish Indies was exploration of an unknown area and claim of sovereignty for the crown conquest of indigenous peoples or assumption of control without direct violence settlement by Spaniards who were awarded the labour of indigenous people via the encomienda and the existing settlements becoming the launch point for further exploration, conquest, and settlement, followed by the establishment institutions with officials appointed by the crown The patterns set in the Caribbean were replicated throughout the expanding Spanish sphere, so although the importance of the Caribbean quickly faded after the Spanish conquest of the Aztec empire and the Spanish conquest of the Incas, many of those participating in those conquests had started their exploits in the Caribbean The first permanent European settlements in the New World were established in the Caribbean, initially on the island of Hispaniola, later Cuba and Puerto Rico As a Genoese with the connections to Portugal, Columbus considered settlement to be on the pattern of trading forts and factories, with salaried employees to trade with locals and to identify exploitable resources However, Spanish settlement in the New World was based on a pattern of a large, permanent settlements with the entire complex of institutions and material life to replicate Castilian life in a different venue Columbus's second voyage in had a large contingent of settlers and goods to accomplish that On Hispaniola, the city of Santo Domingo was founded in by Christopher Columbus's brother Bartholomew Columbus and became a stone built, permanent city The early history of the first settlements are deeply entwined with Christopher Columbus and his extended family and the crown's attempts to limit the expansive powers granted by the crown's first contract with Columbus, the Capitulations of Santa Fe Although Columbus staunchly asserted and believed that the lands he encountered were in Asia, the paucity of material wealth and the relative lack of complexity of indigenous society meant that the Crown of Castile initially was not concerned with the extensive powers granted Columbus However, as the Caribbean became a draw for Spanish settlement and as Columbus and his extended Genoese family failed to be recognized as officials worthy of the titles they held, there was unrest Catholic Monarchs reacted when Columbus encountered the mainland in They learned of his discovery in May , and, taking advantage of a revolt against Columbus in Hispaniola, they appointed Francisco de Bobadilla as governor of the Indies with civil and criminal jurisdiction over the lands discovered by Columbus He, however, was soon replaced by Nicolás de Ovando in September Henceforth, the Crown would authorize to individuals voyages to discover territories in the Indies only with previous royal license, and since , the monopoly of the Crown was assured by the establishment of Casa de Contratación House of Trade at Seville But the successors of Columbus litigated against the Crown until for the fulfillment of the Capitulations of Santa Fe in the pleitos colombinos Spanish territories in the New World around In metropolitan Spain, the direction of the issues of the Indies was taken over by the Bishop Fonseca between and , and again between and , after a brief period of Jean le Sauvage After the figure of the secretary was added, so then between and Gaspar de Gricio took charge, between and Lope de Conchillos followed him, and since , Francisco de los Cobos In , the Junta of The Indies was constituted as a standing committee belonging to the Council of Castile to address issues of the Indies, and this junta constituted the origin of the Council of the Indies in Following the settlement of Hispaniola which was successful towards the end of the s, the settlers began searching elsewhere to begin new settlements, since there was little apparent wealth and the numbers of indigenous were declining Those from the less prosperous Hispaniola were eager to search for new success in a new settlement From there Juan Ponce de León conquered Puerto Rico and Diego Velázquez took Cuba In , the Board of Navigators met in Burgos concurred the need to establish settlements on the mainland, a project entrusted to Alonso de Ojeda and Diego de Nicuesa as governors, subordinated to the governor of Hispaniola, who was the newly appointed Diego Columbus, with the same legal authority that Ovando The first settlement on the mainland was Santa María la Antigua del Darién in Castilla de Oro now Nicaragua, Costa Rica, Panama and Colombia , settled by Vasco Núñez de Balboa in In , Balboa crossed the Isthmus of Panama, and led the first European expedition to see the Pacific Ocean from the West coast of the New World In an action with enduring historical import, Balboa claimed the Pacific Ocean and all the lands adjoining it for the Spanish Crown The judgment of Seville of May recognized the viceregal title to Diego Columbus, but limited it to Hispaniola and to the islands discovered by his father, Christopher Columbus, nevertheless his power was limited by royal officers and magistrates constituting a dual regime of government Therefore, the king Ferdinand II of Aragon as regent of his daughter the queen Joanna separated the territories of mainland, designated as Castilla de Oro, from the viceroy of Hispaniola, establishing as General Lieutenant to Pedrarias Dávila in with functions similar to those of a viceroy, remaining Balboa subordinated as governing of Panama and Coiba on the Pacific Coast, and that after his death returned to Castilla de Oro The territory of Castilla de Oro did not include either Veragua which was comprised approximately between the river Chagres and cape Gracias a Dios , due to this territory was subject to a lawsuit between the Crown and Diego Columbus, or the region farther north, towards the Yucatán peninsula, explored by Yáñez Pinzón and Solís in – , due to its remoteness The conflicts of the viceroy Columbus with the royal officers and with the Audiencia, created in Santo Domingo in , caused his return to the Peninsula in Campaigns in Africa edit After the conquest of Melilla in , the Spanish expansionist policy in North Africa was developed during the regency of Ferdinand the Catholic in Castile, stimulated by the Cardinal Cisneros, once the Reconquista in the Iberian Peninsula was finished That way, several towns and outposts in the North African coast were conquered and occupied by Castile Mazalquivir , Peñón de Vélez de la Gomera , Oran , Algiers , Bugia , and Tripoli In the Atlantic coast, Spain took possession of the outpost of Santa Cruz de la Mar Pequeña with support from the Canary Islands, and it was retained until with the consent of the treaty of Cintra The Spanish Habsburgs The Sun Never Sets – edit Further information Habsburg Spain, Spanish Habsburgs and Iberian Union The period of the th to the mid th century is known as the Golden Age of Spain in Spanish, Siglo de Oro As a result of the marriage politics of the Catholic Monarchs in Spanish, Reyes Católicos , their Habsburg grandson Charles inherited the Castilian empire in America, the Possessions of the Crown of Aragon in the Mediterranean including a large portion of modern Italy , lands in Germany, the Low Countries, Franche Comté, and Austria this one, along with the rest of hereditary Habsburg domains was almost immediately transferred to Ferdinand, the Emperor's brother While not directly an inheritance, Charles was elected emperor of the Holy Roman Empire after the death of his grandfather Emperor Maximilian thanks to prodigious bribes paid the prince electors Charles became the most powerful man in Europe, his rule stretching over an empire in Europe unrivaled in extent until the Napoleonic era It was often said during this time that it was the empire on which the sun never set This sprawling overseas empire of the Spanish Golden Age was controlled, not from inland Valladolid, but from Seville, citation needed where the Casa de Contratación House of Trade regulated commerce with the Indies, as well as licenses for emigration The supreme body for administering the Indies was the Council of the Indies, established in The Castilian Empire abroad was initially a disappointment It

stable for several days, slowly decomposing to the metal amide and dihydrogen Most studies involving liquid ammonia solutions are done in reducing conditions although oxidation of liquid ammonia is usually slow, there is still a risk of explosion, particularly if transition metal ions are present as possible catalysts Ammonia's role in biological systems and human disease edit Main symptoms of hyperammonemia ammonia reaching toxic concentrations Ammonia is both a metabolic waste and a metabolic input throughout the biosphere It is an important source of nitrogen for living systems Although atmospheric nitrogen abounds more than % , few living creatures are capable of using this atmospheric nitrogen in its diatomic form, N gas Therefore, nitrogen fixation is required for the synthesis of amino acids, which are the building blocks of protein Some plants rely on ammonia and other nitrogenous wastes incorporated into the soil by decaying matter Others, such as nitrogen fixing legumes, benefit from symbiotic relationships with rhizobia that create ammonia from atmospheric nitrogen Biosynthesis edit In certain organisms, ammonia is produced from atmospheric nitrogen by enzymes called nitrogenases The overall process is called nitrogen fixation Although it is unlikely that biomimetic methods that are competitive with the Haber process will be developed, citation needed intense effort has been directed toward understanding the mechanism of biological nitrogen fixation The scientific interest in this problem is motivated by the unusual structure of the active site of the enzyme, which consists of an Fe MoS ensemble Ammonia is also a metabolic product of amino acid deamination catalyzed by enzymes such as glutamate dehydrogenase Ammonia excretion is common in aquatic animals In humans, it is quickly converted to urea, which is much less toxic, particularly less basic This urea is a major component of the dry weight of urine Most reptiles, birds, insects, and snails excrete uric acid solely as nitrogenous waste In physiology edit Ammonia also plays a role in both normal and abnormal animal physiology It is biosynthesised through normal amino acid metabolism and is toxic in high concentrations The liver converts ammonia to urea through a series of reactions known as the urea cycle Liver dysfunction, such as that seen in cirrhosis, may lead to elevated amounts of ammonia in the blood hyperammonemia Likewise, defects in the enzymes responsible for the urea cycle, such as ornithine transcarbamylase, lead to hyperammonemia Hyperammonemia contributes to the confusion and coma of hepatic encephalopathy, as well as the neurologic disease common in people with urea cycle defects and organic acidurias Ammonia is important for normal animal acid base balance After formation of ammonium from glutamine, a ketoglutarate may be degraded to produce two molecules of bicarbonate, which are then available as buffers for dietary acids Ammonium is excreted in the urine, resulting in net acid loss Ammonia may itself diffuse across the renal tubules, combine with a hydrogen ion, and thus allow for further acid excretion Excretion edit Main article Excretion Ammonium ions are a toxic waste product of metabolism in animals In fish and aquatic invertebrates, it is excreted directly into the water In mammals, sharks, and amphibians, it is converted in the urea cycle to urea, because it is less toxic and can be stored more efficiently In birds, reptiles, and terrestrial snails, metabolic ammonium is converted into uric acid, which is solid, and can therefore be excreted with minimal water loss Reference ranges for blood tests, comparing blood content of ammonia shown in yellow near middle with other constituents In astronomy edit Ammonia occurs in the atmospheres of the outer gas planets such as Jupiter % ammonia and Saturn % ammonia Ammonia has been detected in the atmospheres of the gas giant planets, including Jupiter, along with other gases like methane, hydrogen, and helium The interior of Saturn may include frozen crystals of ammonia It is naturally found on Deimos and Phobos – the two moons of Mars Interstellar space edit Ammonia was first detected in interstellar space in , based on microwave emissions from the direction of the galactic core This was the first polyatomic molecule to be so detected The sensitivity of the molecule to a broad range of excitations and the ease with which it can be observed in a number of regions has made ammonia one of the most important molecules for studies of molecular clouds The relative intensity of the ammonia lines can be used to measure the temperature of the emitting medium The following isotopic species of ammonia have been detected NH , NH , NH D, NHD , and ND The detection of triply deuterated ammonia was considered a surprise as deuterium is relatively scarce It is thought that the low temperature conditions allow this molecule to survive and accumulate Since its interstellar discovery, NH has proved to be an invaluable spectroscopic tool in the study of the interstellar medium With a large number of transitions sensitive to a wide range of excitation conditions, NH has been widely astronomically detected – its detection has been reported in hundreds of journal articles Listed below is a sample of journal articles that highlights the range of detectors that have been used to identify ammonia The study of interstellar ammonia has been important to a number of areas of research in the last few decades Some of these are delineated below and primarily involve using ammonia as an interstellar thermometer Interstellar formation mechanisms edit Ball and stick model of the diamminesilver I cation, Ag NH + The interstellar abundance for ammonia has been measured for a variety of environments The NH H ratio has been estimated to range from - in small dark clouds up to - in the dense core of the Orion Molecular Cloud Complex Although a total of total production routes have been proposed, the principal formation mechanism for interstellar NH is the reaction NH + + e- ? NH + H• The rate constant, k, of this reaction depends on the temperature of the environment, with a value of × - at K The rate constant was calculated from the formula k a T B For the primary formation reaction, a × - and B - Assuming an NH + abundance of × - and an electron abundance of - typical of molecular clouds, the formation will proceed at a rate of × - cm- s- in a molecular cloud of total density cm- All other proposed formation reactions have rate constants of between and orders of magnitude smaller, making their contribution to the abundance of ammonia relatively insignificant As an example of the minor contribution other formation reactions play, the reaction H + NH ? NH + H has a rate constant of × - Assuming H densities of and NH H ratio of - , this reaction proceeds at a rate of × - , more than orders of magnitude slower than the primary reaction above Some of the other possible formation reactions are H- + NH + ? NH + H PNH + + e- ? P + NH Interstellar destruction mechanisms edit There are total proposed reactions leading to the destruction of NH Of these, were tabulated in extensive tables of the chemistry among C, N, and O compounds A review of interstellar ammonia cites the following reactions as the principal dissociation mechanisms NH + H + ? NH + + H NH + HCO+ ? NH + + CO with rate constants of × - and × - , respectively The above equations , run at a rate of × - and × - , respectively These calculations assumed the given rate constants and abundances of NH H - , H + H × - , HCO+ H × - , and total densities of n , typical of cold, dense, molecular clouds Clearly, between these two primary reactions, equation is the dominant destruction reaction, with a rate ~ , times faster than equation This is due to the relatively Because of its many uses, ammonia is one of the most highly produced inorganic chemicals There are numerous large scale ammonia production plants worldwide, producing a total of million tonnes of nitrogen equivalent to million tonnes of ammonia in China produced % of the worldwide production, followed by India with %, Russia with %, and the United States with % % or more of the ammonia produced is used for fertilizing agricultural crops Ammonia is also used for the production of plastics, fibers, explosives, nitric acid via the Ostwald process and intermediates for dyes and pharmaceuticals Contents hide History Modern ammonia producing plants Sustainable ammonia production See also References External links History edit Before the start of World War I, most ammonia was obtained by the dry distillation of nitrogenous vegetable and animal products by the reduction of nitrous acid and nitrites with hydrogen and also by the decomposition of ammonium salts by alkaline hydroxides or by quicklime, the salt most generally used being the chloride sal ammoniac Today, most ammonia is produced on a large scale by the Haber process with capacities of up to , metric tons per day Ammonia is manufactured on a large scale by Haber's process In this process,N and H gases are allowed to react at high pressure of bar a Modern ammonia producing plants edit Block flow diagram of the ammonia synthesis process A typical modern ammonia producing plant first converts natural gas i e , methane or LPG liquefied petroleum gases such as propane and butane or petroleum naphtha into gaseous hydrogen The method for producing hydrogen from hydrocarbons is referred to as Steam Reforming The hydrogen is then combined with nitrogen to produce ammonia via the Haber Bosch process Starting with a natural gas feedstock, the processes used in producing the hydrogen are The first step in the process is to remove sulfur compounds from the feedstock because sulfur deactivates the catalysts used in subsequent steps Sulfur removal requires catalytic hydrogenation to convert sulfur compounds in the feedstocks to gaseous hydrogen sulfide H + RSH ? RH + H S gas The gaseous hydrogen sulfide is then adsorbed and removed by passing it through beds of zinc oxide where it is converted to solid zinc sulfide H S + ZnO ? ZnS + H O Catalytic steam reforming of the sulfur free feedstock is then used to form hydrogen plus carbon monoxide CH + H O ? CO + H The next step then uses catalytic shift conversion to convert the carbon monoxide to carbon dioxide and more hydrogen CO + H O ? CO + H The carbon dioxide is then removed either by absorption in aqueous ethanolamine solutions or by adsorption in pressure swing adsorbers PSA using proprietary solid adsorption media The final step in producing the hydrogen is to use catalytic methanation to remove any small residual amounts of carbon monoxide or carbon dioxide from the hydrogen CO + H ? CH + H O CO + H ? CH + H O To produce the desired end product ammonia, the hydrogen is then catalytically reacted with nitrogen derived from process air to form anhydrous liquid ammonia This step is known as the ammonia synthesis loop also referred to as the Haber Bosch process H + N ? NH Due to the nature of the typically multi promoted magnetite catalyst used in the ammonia synthesis reaction, only very low levels of oxygen containing especially CO, CO and H O compounds can be tolerated in the synthesis hydrogen and nitrogen mixture gas Relatively pure nitrogen can be obtained by Air separation, but additional oxygen removal may be required Hydrogen storage From Wikipedia, the free encyclopedia Utility scale underground liquid hydrogen storage Methods of hydrogen storage for subsequent use span many approaches, including high pressures, cryogenics, and chemical compounds that reversibly release H upon heating Underground hydrogen storage is useful to provide grid energy storage for intermittent energy sources, like wind power, as well as providing fuel for transportation, particularly for ships and airplanes Most research into hydrogen storage is focused on storing hydrogen as a lightweight, compact energy carrier for mobile applications Liquid hydrogen or slush hydrogen may be used, as in the Space Shuttle However liquid hydrogen requires cryogenic storage and boils around K - °C or - °F Hence, its liquefaction imposes a large energy loss as energy is needed to cool it down to that temperature The tanks must also be well insulated to prevent boil off but adding insulation increases cost Liquid hydrogen has less energy density by volume than hydrocarbon fuels such as gasoline by approximately a factor of four This highlights the density problem for pure hydrogen there is actually about % more hydrogen in a liter of gasoline grams hydrogen than there is in a liter of pure liquid hydrogen grams hydrogen The carbon in the gasoline also contributes to the energy of combustion Compressed hydrogen, by comparison, is stored quite differently Hydrogen gas has good energy density by weight, but poor energy density by volume versus hydrocarbons, hence it requires a larger tank to store A large hydrogen tank will be heavier than the small hydrocarbon tank used to store the same amount of energy, all other factors remaining equal Increasing gas pressure would improve the energy density by volume, making for smaller, but not lighter container tanks see hydrogen tank Compressed hydrogen costs % of the energy content to power the compressor Higher compression without energy recovery will mean more energy lost to the compression step Compressed hydrogen storage can exhibit very low permeation Contents hide Automotive Onboard hydrogen storage Established technologies Compressed hydrogen Liquid hydrogen Proposals and research Chemical storage Metal hydrides Non metal hydrides Carbohydrates Synthesized hydrocarbons Liquid organic hydrogen carriers LOHC Ammonia Amine borane complexes Imidazolium ionic liquids Phosphonium borate Carbonite substances Metal organic frameworks Encapsulation Physical storage Cryo compressed Carbon nanotubes Clathrate hydrates Glass capillary arrays Glass microspheres Stationary hydrogen storage Underground hydrogen storage Power to gas See also References External links Automotive Onboard hydrogen storage edit Timeline Targets assume a kg hydrogen storage system Targets were set by the FreedomCAR Partnership in January between the United States Council for Automotive Research USCAR and U S DOE Targets assume a kg H storage system The targets were not reached in The targets were revised in to reflect new data on system efficiencies obtained from fleets of test cars The ultimate goal for volumetric storage is still above the theoretical density of liquid hydrogen It is important to note that these targets are for the hydrogen storage system, not the hydrogen storage material System densities are often around half those of the working material, thus while a material may store wt% H , a working system using that material may only achieve wt% when the weight of tanks, temperature and pressure control equipment, etc , is considered In , only two storage technologies were identified as being susceptible to meet DOE targets MOF exceeds target for volumetric capacity, while cryo compressed H exceeds more restrictive targets for both gravimetric and volumetric capacity see slide in Established technologies edit net storage density of hydrogen Compressed hydrogen edit Compressed hydrogen is the gaseous state of the element hydrogen which is kept under pressure Compressed hydrogen in hydrogen tanks at bar , psi and bar , psi is used for hydrogen tank systems in vehicles, based on type IV carbon composite technology Car manufacturers have been developing this solution, such as Honda or Nissan Liquid hydrogen edit BMW has been working on liquid tank for cars, producing for example the BMW Hydrogen Proposals and research edit Hydrogen storage technologies can be divided into physical storage, where hydrogen molecules are stored including pure hydrogen storage via compression and liquefication , and chemical storage, where hydrides are stored Chemical storage edit Chemical storage could offer high storage performance due to the strong interaction However, the regeneration of storage material is still an issue A large number of chemical storage systems are under investigation, which involve hydrolysis reactions, hydrogenation dehydrogenation reactions, ammonia borane and other boron hydrides, ammonia, and alane etc Metal hydrides edit Metal hydride hydrogen storage Metal hydrides, such as MgH , NaAlH , LiAlH , LiH, LaNi H , TiFeH and palladium hydride, with varying degrees of efficiency, can be used as a storage medium for hydrogen, often reversibly Some are easy to fuel liquids at ambient temperature and pressure, others are solids which could be turned into pellets These materials have good energy density by volume, although their energy density by weight is often worse than the leading hydrocarbon fuels Most metal hydrides bind with hydrogen very strongly As a result, high temperatures around °C °F – °C °F are required to release their hydrogen content This energy cost can be reduced by using alloys which consists of a strong hydride former and a weak one such as in LiNH , LiBH and NaBH These are able to form weaker bonds, thereby requiring less input to release stored hydrogen However, if the interaction is too weak, the pressure needed for rehydriding is high, thereby eliminating any energy savings The target for onboard hydrogen fuel systems is roughly < °C for release and < bar for recharge – kJ mol H An alternative method for reducing dissociation temperatures is doping with activators This has been successfully used for aluminium hydride but its complex synthesis makes it undesirable for most applications as it is not easily recharged with hydrogen Currently the only hydrides which are capable of achieving the wt % gravimetric goal for see chart above are limited to lithium, boron and aluminium based compounds at least one of the first row elements or Al must be added Research is being done to determine new compounds which can be used to meet these requirements Proposed hydrides for use in a hydrogen economy include simple hydrides of magnesium or transition metals and complex metal hydrides, typically containing sodium, lithium, or calcium and aluminium or boron Hydrides chosen for storage applications provide low reactivity high safety and high hydrogen storage densities Leading candidates are lithium hydride, sodium borohydride, lithium aluminium hydride and ammonia borane A French company McPhy Energy is developing the first industrial product, based on magnesium hydride, already sold to some major clients such as Iwatani and ENEL New Scientist stated that Arizona State University is investigating using a borohydride solution to store hydrogen, which is released when the solution flows over a catalyst made of ruthenium Researchers at University of Pittsburgh and Georgia Tech performed extensive benchmarking simulations on mixtures of several light metal hydrides to predict possible reaction thermodynamics for hydrogen storage Beyond research, Fuel Cell Company Intelligent Energy has released a small Fuel Cell portable power product 'UPP' which uses metal hydride as the storage media See http www beupp com technical specification Non metal hydrides edit The Italian catalyst manufacturer Acta has proposed using hydrazine as an alternative to hydrogen in fuel cells As the hydrazine fuel is liquid at room temperature, it can be handled and stored more easily than hydrogen By storing it in a tank full of a double bonded carbon oxygen carbonyl, it reacts and forms a safe solid called hydrazone By then flushing the tank with warm water, the liquid hydrazine hydrate is released Hydrazine breaks down in the cell to form nitrogen and hydrogen which bonds with oxygen, releasing water Carbohydrates edit Carbohydrates polymeric C H O releases H in a bioreformer mediated by the enzyme cocktail—cell free synthetic pathway biotransformation Carbohydrate provides high hydrogen storage densities as a liquid with mild pressurization and cryogenic constraints It can also be stored as a solid powder Carbohydrate is the most abundant renewable bioresource in the world In May biochemical engineers from the Virginia Polytechnic Institute and State University and biologists and chemists from the Oak Ridge National Laboratory announced a method of producing high yield pure hydrogen from starch and water In , they demonstrated to produce nearly moles of hydrogen per glucose unit from cellulosic materials and water Thanks to complete conversion and modest reaction conditions, they propose to use carbohydrate as a high energy density hydrogen carrier with a density of wt% Synthesized hydrocarbons edit An alternative to hydrides is to use regular hydrocarbon fuels as the hydrogen carrier Then a small hydrogen reformer would extract the hydrogen as needed by the fuel cell However, these reformers are slow to react to changes in demand and add a large incremental cost to the vehicle powertrain Direct methanol fuel cells do not require a reformer, but provide a lower energy density compared to conventional fuel cells, although this could be counterbalanced with the much better energy densities of ethanol and methanol over hydrogen Alcohol fuel is a renewable resource Solid oxide fuel cells can operate on light hydrocarbons such as propane and methane without a reformer, or can run on higher hydrocarbons with only partial reforming, but the high temperature and slow startup time of these fuel cells are problematic for automotive applications Liquid organic hydrogen carriers LOHC edit Reversible hydrogenation of N Ethylcarbazole Unsaturated organic compounds can store huge amounts of hydrogen These Liquid Organic Hydrogen Carriers LOHC are hydrogenated for storage and dehydrogenated again when the energy hydrogen is needed Researches on LOHC was