text:
I'm Gonna Sit Right Down and Write Myself a Letter
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"I'm Gonna Sit Right Down and Write Myself a Letter" is a 1935 popular song with music by Fred E. Ahlert and lyrics by Joe Young.[1] It has been recorded many times, and has become a standard of the Great American Songbook. It was popularized by Fats Waller, who recorded it in 1935 at the height of his fame.[2]
It is one of several songs from the Harlem Renaissance featured in the Broadway musical Ain't Misbehavin'.
American Public Media's business-news program, Marketplace, uses a portion of Fats Waller's version to open its weekly letters-from-listeners segment.
Recordings[edit]
The song had a major revival in 1957 in a Coral recording (on April 3) by Billy Williams with orchestra directed by Dick Jacobs.[3] It reached #3 on the Billboard magazine charts.[4] A reported million-seller,[5] it was awarded a Gold record.[6]
The song was recorded by Frank Sinatra for his 1954 album Swing Easy, by Bing Crosby for his 1957 LP Bing with a Beat and again by Sinatra in 1962 for his collaborative album with Count Basie, Sinatra–Basie: An Historic Musical First.
Among other versions are recordings by The Boswell Sisters, Connee Boswell, Nat "King" Cole, Scatman Crothers, Gregory Isaacs, Barry Manilow, Dean Martin, Anne Murray, Willie Nelson, Linda Scott, Shakin' Stevens and Sarah Vaughan.
Charlie Gracie (mostly known for his 1957 #1 hit "Butterfly" on Cameo Record label #105—45rpm) recorded "I'm Gonna Sit Right Down and Write Myself a Letter" (Cadillac Record label #141—45 rpm). The flip side of the record was a song written by Gracie, "Boogie Woogie Blues". Gracie's version was released in 1953.[7]
Bill Haley & His Comets recorded a rock and roll version of the song in 1957.[8]
Fabian recorded his version of the song in 1960 on Chancellor Records.[9]
In 1973 Cleo Laine included the song as her opening song on the album I Am a Song[10] and sang on stage during her subsequent tour.
New Jersey entertainer Uncle Floyd (aka Floyd Vivino) has covered this song in his live performances as well as recording it.[11]
Madeleine Peyroux also covered this song on her debut album Dreamland (1996).
In 2012 Paul McCartney covered it on his album of standards, Kisses on the Bottom and chose one of its lines as the title.
References[edit]
Jump up ^ "I'm Gonna Sit Right Down And Write Myself A Letter Lyrics". MetroLyrics > Paul McCartney Lyrics. MetroLyrics. Archived from the original on 4 May 2016. Retrieved 10 October 2016. Songwriters AHLERT, FRED E. / YOUNG, JOE
Jump up ^ Whitburn, Joel (1986). Joel Whitburn's Pop Memories 1890-1954. Wisconsin, USA: Record Research Inc. p. 436. ISBN 0-89820-083-0.
Jump up ^ "Discogs.com". Discogs.com. Retrieved June 6, 2017.
Jump up ^ Whitburn, Joel (2004). The Billboard Book of Top 40 Hits (8th Edition ed.). New York: Billboard Books. p. 679. ISBN 0-8230-7499-4. CS1 maint: Extra text (link)
Jump up ^ Murrells, Joseph (1978). The Book of Golden Discs. London: Barrie and Jenkins. p. 97. ISBN 0214205126.
Jump up ^ "Golden Wax: Awards Go to 4 Coral Top Artists". Billboard. October 28, 1957. p. 22.
Jump up ^ "45cat.com". 45cat.com. Retrieved June 6, 2017.
Jump up ^ "45cat.com". 45cat.com. Retrieved June 6, 2017.
Jump up ^ "45cat.com". 45cat.com. Retrieved June 6, 2017.
Jump up ^ "Discogs.com". Discogs.com. Retrieved June 6, 2017.
Jump up ^ "45cat.com". 45cat.com. Retrieved June 6, 2017.
[show]
v
t
e
The Boswell Sisters
Martha Boswell
Connee Boswell
Helvetia Boswell
Singles
"I Found a Million Dollar Baby"
"Between the Devil and the Deep Blue Sea"
"Dinah"
"Alexander's Ragtime Band"
"St. Louis Blues"
"Cheek to Cheek"
"I'm Gonna Sit Right Down and Write Myself a Letter"
Book:The Boswell Sisters
[show]
v
t
e
Connee Boswell
Singles
"Say It Isn't So"
"Moon Over Miami"
"Basin Street Blues"
"I Let a Song Go Out of My Heart"
"Alexander's Ragtime Band"
"Let It Snow! Let It Snow! Let It Snow!"
"You Were Meant for Me"
"Singin' the Blues"
"I'm Gonna Sit Right Down and Write Myself a Letter"
"If I Give My Heart to You"
Related topics
The Boswell Sisters
Book:Connee Boswell
[show]
v
t
e
Willie Nelson singles discography
1950s
and
1960s
1957
"No Place For Me" / "Lumberjack"
1959
"Man With the Blues" / "The Storm Has Just Begun"
1960
"What a Way to Live" / "Misery Mansion"
"Nite Life" / "Rainy Day Blues"
1961
"The Part Where I Cry" / "Mr. Record Man"
1962
"Willingly" / "Chain of Love"
"Touch Me" / "Where My House Lives"
"Wake Me When It's Over" / "There's Gonna Be Love In My House"
"You Dream About Me" / "Is This My Destiny"
1963
"Half a Man" / "The Last Letter"
"Take My Word" / "Feed it a Memory"
1964
"How Long is Forever" / "You Took My Happy Away"
"Am I Blue" / "There'll Be No Teardrops Tonight"
"River Boy" / "Opportunity to Cry"
"I Never Cared For You" / "You Left Me (A Long Time Ago)"
"Pretty Paper" / "What A Merry Christmas This Could Be"
1965
"She's Not For You" / "Permanently Lonely"
"Healing Hands of Time" / "One Day at the Time"
"I Just Can't Let You Say Goodbye" / "And So Will You, My Love"
1966
"One In A Row" / "San Antonio Rose"
"Colombus Stockade Blues" / "He Sits at my Table"
"I'm Still Not Over You"/ "I Love You Because"
1967
"The Party's Over" / "Make Way for a Better Man"
"Blackjack County Chain" / "Some Other World"
"San Antonio" / "To Make a Long Story Short"
1968
"Little Things" / " Sweet Memories"
"Good Times" / "Where Do You Stand"
"Johnny One Time" / "She's Still Gone"
1969
"Bring Me Sunshine" / "Don't Say Love or Nothing"
"I Hope So" / "Right or Wrong"
1970s
1970
"Once More With Feeling" / "Who Do I Know in Dallas"
"Laying My Burdens Down" / "Truth Number One"
1971
"I'm a Memory" / "Fire and Rain"
"Yesterday's Wine" / "Me and Paul"
1972
"Words Don't Fit the Picture" / "A Moment"
1973
"Shotgun Willie" (mono) / "Sad Songs and Waltzes"
"Stay All Night (Stay a Little Longer)" / "Devil in a Sleepin' Bag"
1974
"I Still Can't Believe You're Gone" / "Heaven and Hell"
"Bloody Mary Morning" / "After the Fire is Gone"(with Tracy Nelson)
"Sister's Comin' Home" (mono) / "Pick Up The Tempo"
1975
"Blue Eyes Crying in the Rain" / "Bandera"
1976
"Remember Me (When the Candle Lights Are Gleaming)" / "Time of the Preacher"
"I'd Have to Be Crazy" (mono) / "Amazing Grace"
"If You've Got the Money I've Got the Time" / "The Sound in Your Mind"
1977
"Uncloudy Day" / "Precious Memories"
"I Love You A Thousand Ways" / "Mom and Dad's Waltz"
1978
"Georgia on My Mind" / "On The Sunny Side Of The Street"
"Blue Skies" / "Moonlight in Vermont"
"All of Me" / "Unchained Melody"
1979
"Whiskey River" / "Under the Double Eagle"
"September Song" / "Don't Get Around Much Anymore"
"White Christmas" / "Blue Christmas"
1980s
1980
"Help Me Make It Through the Night" / "The Pilgrim, Chapter 33"
"My Heroes Have Always Been Cowboys" / "Rising Stars"
"Midnight Rider" / "So You Think You're A Cowboy"
"On the Road Again"/ "Jumpin' Cotton Eyed Joe"(performed by Johnny Gimble)
1981
"Angel Flying Too Close to the Ground" / "I Guess I've Come to Live Here in Your Eyes"
"Mona Lisa" / "Twinkle, Twinkle Little Star"
"I'm Gonna Sit Right Down and Write Myself a Letter" / "Over the Rainbow"
"Heartaches of a Fool" / "Uncloudy Day"
1982
"Always on My Mind" / "The Party's Over"
"Let It Be Me" / "Permanently Lonely"
"Last Thing I Needed First Thing This Morning" / "Old Fords and a Natural Stone"
1983
"Little Old Fashioned Karma" / "Beer Barrel Polka"
"Why Do I Have to Choose" / "Would You Lay with Me (In a Field of Stone)"
"Take It to the Limit" / "Till I Gain Control Again"
"Without a Song"
1984
"City of New Orleans (Unedited version)" / "Why Are You Pickin' On Me"
1985
"Forgiving You Was Easy" / "You Wouldn't Cross the Street"
"Me and Paul" / "I Let My Mind Wander"
1986
"Living in the Promiseland" / "Bach Minuet in G"
"I'm Not Trying to Forget You" / "I've Got the Craziest Feeling"
1987
"Partners After All" / "Home Away From Home"
"Heart of Gold" / "So Much Like My Dad"
"Island in the Sea" / "There Is No Easy Way"
1988
"Nobody There But Me" / "Wake Me When It's Over"
"Spanish Eyes" (with Julio Iglesias) / "Ole Buttermilk Sky"
"Twilight Time" / "Ac-Cent-Tchu-Ate the Positive"
1989
"Nothing I Can Do About It Now" / "If I Were a Painting"
"There You Are" / "Spirit"
"Is The Better Part Over" / "Mr. Record Man"
1990s
1990
"The Highway" / "Spirit"
"Ain't Necessarily So" / "I Never Cared For You" ("Ain't Necessarily So" also on CD Single)
1991
"The Piper Came Today" / "(I Don't Have a Reason) To Go To California Anymore" ("The Piper Came Today" also on CD Single)
"Ten With a Two" / "You Decide"
1993
"Graceland"
"Still is Still Moving to Me" / "Valentine"
1995
"Turn Me Loose and Let Me Swing"
1998
"I Never Cared for You"
2000s
and
2010s
2002
"Mendocino County Line" (with Lee Ann Womack) / "Maria (Shut Up and Kiss Me)" (Both single tracks released on CD and 7" record)
2003
"Wurlitzer Prize" (with Norah Jones)
"Beer for My Horses" (with Toby Keith)
2005
"I'm a Worried Man" (with Toots Hibbert)
"The Harder They Come"
2006
"You Don't Know Me"
"Cowboys Are Frequently, Secretly Fond of Each Other"
2008
"Gravedigger"
"You Don't Think I'm Funny Anymore"
2011
"The Scientist"
2012
"Roll Me Up and Smoke Me When I Die"
"Just Breathe"
"Come On Back Jesus"
2013
"From Here to the Moon and Back" (with Dolly Parton)
"Grandma's Hands" (with Mavis Staples)
"It Won't Be Long" (with The Secret Sisters)
"Somewhere Between" (with Loretta Lynn)
2014
"The Wall"
"Bring It On"
"Laws of Nature"
"Who'll Buy My Memories"
2015
"It's All Going to Pot"
Book:Willie Nelson
Category:Willie Nelson
[show]
v
t
e
Barry Manilow singles
1970s
"Mandy" (1974)
"Sandra" (1974)
"It's a Miracle" (1975)
"Could It Be Magic" (1975)
"I Write the Songs" (1975)
"Tryin' to Get the Feeling Again" (1976)
"This One's for You" (1976)
"Weekend in New England" (1976)
"Looks Like We Made It" (1977)
"Daybreak" (1977)
"It's Just Another New Year's Eve" (1977)
"Can't Smile Without You" (1978)
"Even Now" (1978)
"Copacabana" (1978)
"Ready to Take a Chance Again" (1978)
"Somewhere in the Night" (1978)
"Ships" (1979)
"When I Wanted You" (1979)
1980s
"I Don't Want to Walk Without You" (1980)
"Bermuda Triangle" (1980)
"I Made It Through the Rain" (1980)
"Lonely Together" (1981)
"The Old Songs" (1981)
"Somewhere Down the Road" (1981)
"Let's Hang On!" (1982)
"Oh Julie" (1982)
"Memory" (1982)
"I'm Gonna Sit Right Down and Write Myself a Letter" (1982)
"Read 'Em and Weep" (1983)
"When October Goes" (1984)
"Run to Me" (1985)
"I'm Your Man" (1986)
"Keep Each Other Warm" (1989)
1990s
"If I Can Dream" (1990)
"I'd Really Love to See You Tonight" (1997)
2000s
"River" (2003)
"Unchained Melody" (2006)
"Love Is a Many-Splendored Thing" (2006)
2010s
"Santa Claus Is Coming to Town" (2012)
Retrieved from "https://en.wikipedia.org/w/index.php?title=I%27m_Gonna_Sit_Right_Down_and_Write_Myself_a_Letter&oldid=784124588"
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1935 songs
1957 singles
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Songs with music by Fred E. Ahlert
Bill Haley songs
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Holocrine
From Wikipedia, the free encyclopedia
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Exocrine Secretion
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Merocrine or eccrine – by exocytosis
Apocrine – by membrane budding (loss of cytoplasm)
Holocrine – by membrane rupture
Holocrine secretion
Holocrine is a term used to classify the mode of secretion in exocrine glands in the study of histology. Holocrine secretions are produced in the cytoplasm of the cell and released by the rupture of the plasma membrane, which destroys the cell and results in the secretion of the product into the lumen.
Holocrine gland secretion is the most damaging (to the cell itself and not to the host which begot the cell) type of secretion, with merocrine secretion being the least damaging and apocrine secretion falling in between.
Examples of holocrine glands include the sebaceous glands of the skin and the meibomian glands of the eyelid. The sebaceous gland is an example of a holocrine gland because its product of secretion (sebum) is released with remnants of dead cells.[1]
References[edit]
Jump up ^ Victor Eroschenko, diFiore's Atlas of Histology with functional correlations, Lippincott Williams & Wilkins, 10th edition, 2005. p. 41
External links[edit]
Diagram at uwa.edu.au
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Epithelial tissue
Cells
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Types
Simple squamous epithelium
Endothelium
Mesothelium
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Respiratory epithelium
Stratified squamous epithelium
Stratified cuboidal epithelium
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Types
Mechanism
Merocrine
Eccrine
Apocrine
Holocrine
Sebaceous
Meibomian
Shape
Tubular gland
Alveolar gland
Secretion
Serous glands
Mucous glands
Components
Myoepithelial cell
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Ducts:
Interlobar
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text:
Just Dropped In (To See What Condition My Condition Was In)
From Wikipedia, the free encyclopedia
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This article needs additional citations for verification. Please help improve this article by adding citations to reliable sources. Unsourced material may be challenged and removed. (August 2008) (Learn how and when to remove this template message)
"Just Dropped In (To See What Condition My Condition Was In)"
Single by Mickey Newbury
from the album Harlequin Melodies
Genre
Psychedelic pop[1]
Songwriter(s)
Mickey Newbury
"Just Dropped In (To See What Condition My Condition Was In)" is a counterculture era song written by Mickey Newbury & first a chart hit for Kenny Rogers and the First Edition in 1968. Said to reflect the LSD experience, the song was intended to be a warning against the danger of using LSD. First recorded on October 10, 1967 by Teddy Hill & the Southern Soul as a single on Rice Records (Rice 5028 b/w "Stagger Lee") and produced by Norro Wilson, Jerry Lee Lewis soon covered the song on his album Soul My Way.
In 1968, "Just Dropped In ..." was a hit for Kenny Rogers and the First Edition (with Kenny Rogers on lead vocals). It was Rogers' first top ten hit on the Billboard charts, where it peaked at number five.[2] The song captures the short-lived psychedelic era of the late 1960s, and stands apart from the country folk harmonies that characterized most of the First Edition's catalog,[3] and got the group their first national TV audience on The Smothers Brothers Comedy Hour.
The song features Rogers on lead vocals and was the group's second single from the band's eponymous album The First Edition. Producer Mike Post reversed a few riffs to create the intro, and the solo played by Glen Campbell was heavily compressed and used a tremolo effect to achieve its sound. Another studio guitarist, Mike Deasy, provided the acoustic lead guitar parts.
When Rogers signed to United Artists Records in the mid-1970s after the group split, he re-recorded the track for his Ten Years of Gold album.
Covers[edit]
Bettye LaVette, Karen Records (KA 1544), 1968, flip side to "Get Away". On that release it is called "What Condition My Condition Is In"
Styvar Manor, British group, 1970, issued as single on Polydor.
Jim Turner of comedy troupe Duck's Breath Mystery Theatre performed (as his character Randee of the Redwoods) a surprisingly faithful version on the Ducks' 1986 album Born To Be Tiled.
Die Haut, 1988, with Nick Cave as guest singer.
Supergrass as a B-Side to their 1995 single Alright/Time
The Raymen, Death-Country/Goth-Americana-Billy band, 1998
Willie Nelson, on his 2001 album "Rainbow Connection" and his 2002 album The Great Divide
Mojo Nixon, 2001
Children of Bodom, melodic death metal band, on the Japanese release of their "Blooddrunk" album as a bonus track and on their 2009 cover album "Skeletons in the Closet"
Tom Jones, on the Deluxe Edition of "Spirit in the Room" in 2012
Murder by Death, Americana band, 2012
the Launderettes, Norwegian rock group, 2013, [4]
The Fantastics, Donegal-based band, 2014.
Sinister Dexter, San Francisco soul/funk group, 2014
White Denim exclusively for the black comedy–crime drama television series Fargo, which played over the credits of the "Did you do this? No, you did it!" episode of the second season in 2015.[5]
Abe Diddy and The Krautboys on the album Follow in 2016
Sharon Jones & The Dap-Kings, on the original motion picture soundtrack for the film Soul Men
Reef for their compilation album Together.[6]
Jeff Walker Und Die Fluffers (former lead singer of Carcass), on album Welcome to Carcass Cuntry
In popular culture (First Edition version)[edit]
The song is featured in a dream sequence from the Coen Brothers' 1998 film The Big Lebowski. Additionally, it plays during the end credits of the 2000 video game Driver 2, the title screen and end credits of the 2013 video game Stick It To The Man, and is featured in the 2010 action movie Faster. It is also used is season 3, episode 1 of Chuck: "Chuck Versus the Pink Slip". A short clip is heard in the 2015 HBO documentary Going Clear: Scientology and the Prison of Belief. It is also on the TV series Fargo, season 2 episode 7.
References[edit]
Jump up ^ Pemberton, Pat (21 May 2013). "10 Artists Who Switched Genres". Rolling Stone. Retrieved 23 July 2016.
Jump up ^ Whitburn, Joel (2004). The Billboard Book of Top 40 Hits: Eighth Edition. Record Research. p. 536.
Jump up ^ "Kenny Rogers | Awards". AllMusic. 1938-08-21. Retrieved 2015-11-23.
Jump up ^ "Getaway - The Launderettes | Songs, Reviews, Credits". AllMusic. Retrieved 2015-11-23.
Jump up ^ "White Denim – "Just Dropped In (To See What Condition My Condition Was In)" (Mickey Newbury Cover)".
Jump up ^ Bush, John. "Together, the Best of Reef". Allmusic. Retrieved 27 June 2013.
[show]
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"She Believes in Me"
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"You Decorated My Life"
"Coward of the County"
"Don't Fall in Love with a Dreamer" (with Kim Carnes)
"Love the World Away"
"Lady"
"I Don't Need You"
"Share Your Love with Me"
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"Through the Years"
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"A Love Song"
"We've Got Tonight" (with Sheena Easton)
"All My Life"
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"Eyes That See in the Dark"
"This Woman"
"Buried Treasure"
"Together Again" (with Dottie West)
"What About Me?" (with Kim Carnes and James Ingram)
"Evening Star"
"Crazy"
"Morning Desire"
"Goodbye Marie"
"Tomb of the Unknown Love"
"Twenty Years Ago"
"Make No Mistake, She's Mine" (with Ronnie Milsap)
"I Prefer the Moonlight"
"The Factory"
"I Don't Call Him Daddy"
"When You Put Your Heart in It"
"Planet Texas"
"The Vows Go Unbroken (Always True to You)"
"Maybe" (with Holly Dunn)
"Love Is Strange" (with Dolly Parton)
"Crazy in Love"
"If You Want to Find Love"
"Ol' Red"
"Mary, Did You Know?" (with Wynonna Judd)
"The Greatest"
"Buy Me a Rose" (with Alison Krauss and Billy Dean)
"He Will, She Knows"
"There You Go Again"
"Homeland"
"I Can't Unlove You"
Guest singles
"What Are We Doin' in Love" (with Dottie West)
"Real Love" (with Dolly Parton)
"If I Ever Fall in Love Again" (with Anne Murray)
Related articles
Discography
The First Edition
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The First Edition (1967)
Ruby, Don't Take Your Love To Town (1969)
Something's Burning (1970)
Tell It All Brother (1970)
Transition (1971)
The Ballad of Calico (1972)
I'm Not Making Music for Money (1974)
Singles
"Just Dropped In (To See What Condition My Condition Was In)"
"But You Know I Love You"
"Ruby, Don't Take Your Love to Town"
"Today I Started Loving You Again"
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Chlorofluorocarbon
From Wikipedia, the free encyclopedia
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Chlorofluorocarbons (CFCs) are fully halogenated paraffin hydrocarbons that contain only carbon (С), chlorine (Cl), and fluorine (F), produced as volatile derivative of methane, ethane, and propane. They are also commonly known by the DuPont brand name Freon. The most common representative is dichlorodifluoromethane (R-12 or Freon-12). Many CFCs have been widely used as refrigerants, propellants (in aerosol applications), and solvents. Because CFCs contribute to ozone depletion in the upper atmosphere, the manufacture of such compounds has been phased out under the Montreal Protocol, and they are being replaced with other products such as hydrofluorocarbons (HFCs)[1] (e.g., R-410A) and R-134a.[2][3]
Contents
[hide]
1 Structure, properties and production
2 Reactions
3 Applications
4 Classes of compounds, nomenclature
4.1 Numbering system
5 History
5.1 Commercial development and use
5.2 Regulation
5.2.1 Regulatory gap
5.2.2 Regulation and DuPont
5.3 Phasing-out of CFCs
5.4 Development of alternatives for CFCs
6 Environmental impacts
7 Tracer of ocean circulation
7.1 CFC and SF6 tracer-derived age of ocean water
7.1.1 Partial pressure and ratio dating techniques
8 Safety
9 References
10 External links
Structure, properties and production[edit]
Main article: Organofluorine chemistry
As in simpler alkanes, carbon in the CFCs bonds with tetrahedral symmetry. Because the fluorine and chlorine atoms differ greatly in size and effective charge from hydrogen and from each other, the methane-derived CFCs deviate from perfect tetrahedral symmetry.[4]
The physical properties of CFCs and HCFCs are tunable by changes in the number and identity of the halogen atoms. In general, they are volatile but less so than their parent alkanes. The decreased volatility is attributed to the molecular polarity induced by the halides, which induces intermolecular interactions. Thus, methane boils at −161 °C whereas the fluoromethanes boil between −51.7 (CF2H2) and −128 °C (CF4). The CFCs have still higher boiling points because the chloride is even more polarizable than fluoride. Because of their polarity, the CFCs are useful solvents, and their boiling points make them suitable as refrigerants. The CFCs are far less flammable than methane, in part because they contain fewer C-H bonds and in part because, in the case of the chlorides and bromides, the released halides quench the free radicals that sustain flames.
The densities of CFCs are higher than their corresponding alkanes. In general, the density of these compounds correlates with the number of chlorides.
CFCs and HCFCs are usually produced by halogen exchange starting from chlorinated methanes and ethanes. Illustrative is the synthesis of chlorodifluoromethane from chloroform:
HCCl3 + 2 HF → HCF2Cl + 2 HCl
The brominated derivatives are generated by free-radical reactions of the chlorofluorocarbons, replacing C-H bonds with C-Br bonds. The production of the anesthetic 2-bromo-2-chloro-1,1,1-trifluoroethane ("halothane") is illustrative:
CF3CH2Cl + Br2 → CF3CHBrCl + HBr
Reactions[edit]
The most important reaction[citation needed] of the CFCs is the photo-induced scission of a C-Cl bond:
CCl3F → CCl2F. + Cl.
The chlorine atom, written often as Cl., behaves very differently from the chlorine molecule (Cl2). The radical Cl. is long-lived in the upper atmosphere, where it catalyzes the conversion of ozone into O2. Ozone absorbs UV-B radiation, so its depletion allows more of this high energy radiation to reach the Earth's surface. Bromine atoms are even more efficient catalysts; hence brominated CFCs are also regulated.
Applications[edit]
CFCs and HCFCs are used in a variety of applications because of their low toxicity, reactivity and flammability. Every permutation of fluorine, chlorine and hydrogen based on methane and ethane has been examined and most have been commercialized. Furthermore, many examples are known for higher numbers of carbon as well as related compounds containing bromine. Uses include refrigerants, blowing agents, propellants in medicinal applications and degreasing solvents.
Billions of kilograms of chlorodifluoromethane are produced annually as precursor to tetrafluoroethylene, the monomer that is converted into Teflon.[5]
Classes of compounds, nomenclature[edit]
Chlorofluorocarbons (CFCs): when derived from methane and ethane these compounds have the formulae CClmF4−m and C2ClmF6−m, where m is nonzero.
Hydro-chlorofluorocarbons (HCFCs): when derived from methane and ethane these compounds have the formula CClmFnH4−m−n and C2ClxFyH6−x−y, where m, n, x, and y are nonzero.
and bromofluorocarbons have formulae similar to the CFCs and HCFCs but also include bromine.
Hydrofluorocarbons (HFCs): when derived from methane, ethane, propane, and butane, these compounds have the respective formulae CFmH4−m, C2FmH6−m, C3FmH8−m, and C4FmH10−m, where m is nonzero.
Numbering system[edit]
Main article: refrigerant § Refrigerants by class
A special numbering system is used for fluorinated alkanes, prefixed with Freon-, R-, CFC- and HCFC-, where the rightmost value indicates the number of fluorine atoms, the next value to the left is the number of hydrogen atoms plus 1, and the next value to the left is the number of carbon atoms less one (zeroes are not stated), and the remaining atoms are chlorine.
Freon-12, for example, indicates a methane derivative (only two numbers) containing two fluorine atoms (the second 2) and no hydrogen (1-1=0). It is therefore CCl2F2.
Another equation that can be applied to get the correct molecular formula of the CFC/R/Freon class compounds is this to take the numbering and add 90 to it. The resulting value will give the number of carbons as the first numeral, the second numeral gives the number of hydrogen atoms, and the third numeral gives the number of fluorine atoms. The rest of the unaccounted carbon bonds are occupied by chlorine atoms. The value of this equation is always a three figure number. An easy example is that of CFC-12, which gives: 90+12=102 -> 1 carbon, 0 hydrogens, 2 fluorine atoms, and hence 2 chlorine atoms resulting in CCl2F2. The main advantage of this method of deducing the molecular composition in comparison with the method described in the paragraph above is that it gives the number of carbon atoms of the molecule.
Freons containing bromine are signified by four numbers. Isomers, which are common for ethane and propane derivatives, are indicated by letters following the numbers :
hidePrincipal CFCs
Systematic name
Common/trivial
name(s), code
Boiling point (°C)
Formula
Trichlorofluoromethane Freon-11, R-11, CFC-11 23.77 CCl3F
Dichlorodifluoromethane Freon-12, R-12, CFC-12 −29.8 CCl2F2
Difluoromethane/pentafluoroethane R-410A, Puron, AZ-20 −48.5 50% CH2F2/50% CHF2CF3
Chlorotrifluoromethane Freon-13, R-13, CFC-13 −81 CClF3
Chlorodifluoromethane R-22, HCFC-22 −40.8 CHClF2
Dichlorofluoromethane R-21, HCFC-21 8.9 CHCl2F
Chlorofluoromethane Freon 31, R-31, HCFC-31 −9.1 CH2ClF
Bromochlorodifluoromethane BCF, Halon 1211, H-1211, Freon 12B1 −3.7 CBrClF2
1,1,2-Trichloro-1,2,2-trifluoroethane Freon 113, R-113, CFC-113, 1,1,2-Trichlorotrifluoroethane 47.7 Cl2FC-CClF2
1,1,1-Trichloro-2,2,2-trifluoroethane Freon 113a, R-113a, CFC-113a 45.9 Cl3C-CF3
1,2-Dichloro-1,1,2,2-tetrafluoroethane Freon 114, R-114, CFC-114, Dichlorotetrafluoroethane 3.8 ClF2C-CClF2
1-Chloro-1,1,2,2,2-pentafluoroethane Freon 115, R-115, CFC-115, Chloropentafluoroethane −38 ClF2C-CF3
2-Chloro-1,1,1,2-tetrafluoroethane R-124, HCFC-124 −12 CHFClCF3
1,1-Dichloro-1-fluoroethane R-141b, HCFC-141b 32 Cl2FC-CH3
1-Chloro-1,1-difluoroethane R-142b, HCFC-142b −9.2 ClF2C-CH3
Tetrachloro-1,2-difluoroethane Freon 112, R-112, CFC-112 91.5 CCl2FCCl2F
Tetrachloro-1,1-difluoroethane Freon 112a, R-112a, CFC-112a 91.5 CClF2CCl3
1,1,2-Trichlorotrifluoroethane Freon 113, R-113, CFC-113 48 CCl2FCClF2
1-bromo-2-chloro-1,1,2-trifluoroethane Halon 2311a 51.7 CHClFCBrF2
2-bromo-2-chloro-1,1,1-trifluoroethane Halon 2311 50.2 CF3CHBrCl
1,1-Dichloro-2,2,3,3,3-pentafluoropropane R-225ca, HCFC-225ca 51 CF3CF2CHCl2
1,3-Dichloro-1,2,2,3,3-pentafluoropropane R-225cb, HCFC-225cb 56 CClF2CF2CHClF
History[edit]
Carbon tetrachloride (CCl4) was used in fire extinguishers and glass "anti-fire grenades" from the late nineteenth century until around the end of World War II. Experimentation with chloroalkanes for fire suppression on military aircraft began at least as early as the 1920s. Freon is a trade name for a group of CFCs which are used primarily as refrigerants, but also have uses in fire-fighting and as propellants in aerosol cans. Bromomethane is widely used as a fumigant. Dichloromethane is a versatile industrial solvent.
The Belgian scientist Frédéric Swarts pioneered the synthesis of CFCs in the 1890s. He developed an effective exchange agent to replace chloride in carbon tetrachloride with fluoride to synthesize CFC-11 (CCl3F) and CFC-12 (CCl2F2).
In the late 1920s, Thomas Midgley, Jr. improved the process of synthesis and led the effort to use CFC as refrigerant to replace ammonia (NH3), chloromethane (CH3Cl), and sulfur dioxide (SO2), which are toxic but were in common use. In searching for a new refrigerant, requirements for the compound were: low boiling point, low toxicity, and to be generally non-reactive. In a demonstration for the American Chemical Society, Midgley flamboyantly demonstrated all these properties by inhaling a breath of the gas and using it to blow out a candle[6] in 1930.[7][8]
Commercial development and use[edit]
During World War II, various chloroalkanes were in standard use in military aircraft, although these early halons suffered from excessive toxicity. Nevertheless, after the war they slowly became more common in civil aviation as well. In the 1960s, fluoroalkanes and bromofluoroalkanes became available and were quickly recognized as being highly effective fire-fighting materials. Much early research with Halon 1301 was conducted under the auspices of the US Armed Forces, while Halon 1211 was, initially, mainly developed in the UK. By the late 1960s they were standard in many applications where water and dry-powder extinguishers posed a threat of damage to the protected property, including computer rooms, telecommunications switches, laboratories, museums and art collections. Beginning with warships, in the 1970s, bromofluoroalkanes also progressively came to be associated with rapid knockdown of severe fires in confined spaces with minimal risk to personnel.
By the early 1980s, bromofluoroalkanes were in common use on aircraft, ships, and large vehicles as well as in computer facilities and galleries. However, concern was beginning to be expressed about the impact of chloroalkanes and bromoalkanes on the ozone layer. The Vienna Convention for the Protection of the Ozone Layer did not cover bromofluoroalkanes as it was thought, at the time, that emergency discharge of extinguishing systems was too small in volume to produce a significant impact, and too important to human safety for restriction.
Regulation[edit]
This section does not cite any sources. Please help improve this section by adding citations to reliable sources. Unsourced material may be challenged and removed. (February 2015) (Learn how and when to remove this template message)
Since the late 1970s, the use of CFCs has been heavily regulated because of their destructive effects on the ozone layer. After the development of his electron capture detector, James Lovelock was the first to detect the widespread presence of CFCs in the air, finding a mole fraction of 60 ppt of CFC-11 over Ireland. In a self-funded research expedition ending in 1973, Lovelock went on to measure CFC-11 in both the Arctic and Antarctic, finding the presence of the gas in each of 50 air samples collected, and concluding that CFCs are not hazardous to the environment. The experiment did however provide the first useful data on the presence of CFCs in the atmosphere. The damage caused by CFCs was discovered by Sherry Rowland and Mario Molina who, after hearing a lecture on the subject of Lovelock's work, embarked on research resulting in the first publication suggesting the connection in 1974. It turns out that one of CFCs' most attractive features—their low reactivity— is key to their most destructive effects. CFCs' lack of reactivity gives them a lifespan that can exceed 100 years, giving them time to diffuse into the upper stratosphere.[9] Once in the stratosphere, the sun's ultraviolet radiation is strong enough to cause the homolytic cleavage of the C-Cl bond.
NASA projection of stratospheric ozone, in Dobson units, if chlorofluorocarbons had not been banned. Animated version.
By 1987, in response to a dramatic seasonal depletion of the ozone layer over Antarctica, diplomats in Montreal forged a treaty, the Montreal Protocol, which called for drastic reductions in the production of CFCs. On 2 March 1989, 12 European Community nations agreed to ban the production of all CFCs by the end of the century. In 1990, diplomats met in London and voted to significantly strengthen the Montreal Protocol by calling for a complete elimination of CFCs by the year 2000. By the year 2010, CFCs should have been completely eliminated from developing countries as well.
Ozone-depleting gas trends
Because the only CFCs available to countries adhering to the treaty is from recycling, their prices have increased considerably. A worldwide end to production should also terminate the smuggling of this material. However, there are current CFC smuggling issues, as recognized by the United Nations Environmental Programme (UNEP) in a 2006 report titled "Illegal Trade in Ozone Depleting Substances". UNEP estimates that between 16,000–38,000 tonnes of CFCs passed through the black market in the mid-1990s. The report estimated between 7,000 and 14,000 tonnes of CFCs are smuggled annually into developing countries. Asian countries are those with the most smuggling; as of 2007, China, India and South Korea were found to account for around 70% of global CFC production,[10] South Korea later to ban CFC production in 2010.[11] Possible reasons for continued CFC smuggling were also examined: the report noted that many banned CFC producing products have long lifespans and continue to operate. The cost of replacing the equipment of these items is sometimes cheaper than outfitting them with a more ozone-friendly appliance. Additionally, CFC smuggling is not considered a significant issue, so the perceived penalties for smuggling are low. In 2018 public attention was drawn to the issue, that at an unknown place in east Asia an estimated amount of 13.000 metric tons anually of CFCs have been produced since about 2012 in violation of the protocol.[12][13] While the eventual phaseout of CFCs is likely, efforts are being taken to stem these current non-compliance problems.
By the time of the Montreal Protocol, it was realised that deliberate and accidental discharges during system tests and maintenance accounted for substantially larger volumes than emergency discharges, and consequently halons were brought into the treaty, albeit with many exceptions.
Regulatory gap[edit]
While the production and consumption of CFCs are regulated under the Montreal Protocol, emissions from existing banks of CFCs are not regulated under the agreement. In 2002, there were an estimated 5,791 kilotons of CFCs in existing products such as refrigerators, air conditioners, aerosol cans and others.[14] Approximately one-third of these CFCs are projected to be emitted over the next decade if action is not taken, posing a threat to both the ozone layer and the climate.[15] A proportion of these CFCs can be safely captured and destroyed.
Regulation and DuPont[edit]
In 1978 the United States banned the use of CFCs such as Freon in aerosol cans, the beginning of a long series of regulatory actions against their use. The critical DuPont manufacturing patent for Freon ("Process for Fluorinating Halohydrocarbons", U.S. Patent #3258500) was set to expire in 1979. In conjunction with other industrial peers DuPont formed a lobbying group, the "Alliance for Responsible CFC Policy," to combat regulations of ozone-depleting compounds.[16] In 1986 DuPont, with new patents in hand, reversed its previous stance and publicly condemned CFCs.[17] DuPont representatives appeared before the Montreal Protocol urging that CFCs be banned worldwide and stated that their new HCFCs would meet the worldwide demand for refrigerants.[17]
Phasing-out of CFCs[edit]
Use of certain chloroalkanes as solvents for large scale application, such as dry cleaning, have been phased out, for example, by the IPPC directive on greenhouse gases in 1994 and by the volatile organic compounds (VOC) directive of the EU in 1997. Permitted chlorofluoroalkane uses are medicinal only.
Bromofluoroalkanes have been largely phased out and the possession of equipment for their use is prohibited in some countries like the Netherlands and Belgium, from 1 January 2004, based on the Montreal Protocol and guidelines of the European Union.
Production of new stocks ceased in most (probably all) countries in 1994.[citation needed] However many countries still require aircraft to be fitted with halon fire suppression systems because no safe and completely satisfactory alternative has been discovered for this application. There are also a few other, highly specialized uses. These programs recycle halon through "halon banks" coordinated by the Halon Recycling Corporation[18] to ensure that discharge to the atmosphere occurs only in a genuine emergency and to conserve remaining stocks.
The interim replacements for CFCs are hydrochlorofluorocarbons (HCFCs), which deplete stratospheric ozone, but to a much lesser extent than CFCs.[19] Ultimately, hydrofluorocarbons (HFCs) will replace HCFCs. Unlike CFCs and HCFCs, HFCs have an ozone depletion potential (ODP) of 0.[20] DuPont began producing hydrofluorocarbons as alternatives to Freon in the 1980s. These included Suva refrigerants and Dymel propellants.[21] Natural refrigerants are climate friendly solutions that are enjoying increasing support from large companies and governments interested in reducing global warming emissions from refrigeration and air conditioning. Hydrofluorocarbons are included in the Kyoto Protocol because of their very high Global Warming Potential and are facing calls to be regulated under the Montreal Protocol[dubious – discuss][22] due to the recognition of halocarbon contributions to climate change.[23]
On 21 September 2007, approximately 200 countries agreed to accelerate the elimination of hydrochlorofluorocarbons entirely by 2020 in a United Nations-sponsored Montreal summit. Developing nations were given until 2030. Many nations, such as the United States and China, who had previously resisted such efforts, agreed with the accelerated phase out schedule.[24]
Development of alternatives for CFCs[edit]
Work on alternatives for chlorofluorocarbons in refrigerants began in the late 1970s after the first warnings of damage to stratospheric ozone were published.
The hydrochlorofluorocarbons (HCFCs) are less stable in the lower atmosphere, enabling them to break down before reaching the ozone layer. Nevertheless, a significant fraction of the HCFCs do break down in the stratosphere and they have contributed to more chlorine buildup there than originally predicted. Later alternatives lacking the chlorine, the hydrofluorocarbons (HFCs) have an even shorter lifetimes in the lower atmosphere.[19] One of these compounds, HFC-134a, is now used in place of CFC-12 in automobile air conditioners. Hydrocarbon refrigerants (a propane/isobutane blend) are also used extensively in mobile air conditioning systems in Australia, the USA and many other countries, as they have excellent thermodynamic properties and perform particularly well in high ambient temperatures.
One of the natural refrigerants (along with ammonia and carbon dioxide), hydrocarbons have negligible environmental impacts and are also used worldwide in domestic and commercial refrigeration applications, and are becoming available in new split system air conditioners.[25] Various other solvents and methods have replaced the use of CFCs in laboratory analytics.[26]
In Metered-dose inhalers (MDI), a non-ozone effecting substitute was developed as a propellant, known as "hydrofluoroalkane."[27]
Applications and replacements for CFCs
Application
Previously used CFC
Replacement
Refrigeration & air-conditioning CFC-12 (CCl2F2); CFC-11(CCl3F); CFC-13(CClF3); HCFC-22 (CHClF2); CFC-113 (Cl2FCCClF2); CFC-114 (CClF2CClF2); CFC-115 (CF3CClF2); HFC-23 (CHF3); HFC-134a (CF3CFH2); HFC-507 (a 1:1 azeotropic mixture of HFC 125 (CF3 CHF2) and HFC-143a (CF3CH3)); HFC 410 (a 1:1 azeotropic mixture of HFC-32 (CF2H2) and HFC-125 (CF3CF2H))
Propellants in medicinal aerosols CFC-114 (CClF2CClF2) HFC-134a (CF3CFH2); HFC-227ea (CF3CHFCF3)
Blowing agents for foams CFC-11 (CCl3F); CFC 113 (Cl2FCCClF2); HCFC-141b (CCl2FCH3) HFC-245fa (CF3CH2CHF2); HFC-365 mfc (CF3CH2CF2CH3)
Solvents, degreasing agents, cleaning agents CFC-11 (CCl3F); CFC-113 (CCl2FCClF2) None
Environmental impacts[edit]
As previously discussed, CFCs were phased out via the Montreal Protocol due to their part in ozone depletion. However, the atmospheric impacts of CFCs are not limited to its role as an active ozone reducer. This anthropogenic compound is also a greenhouse gas, with a much higher potential to enhance the greenhouse effect than CO2.
Infrared absorption bands trap heat from escaping earth's atmosphere. In the case of CFCs, the strongest of these bands are located in the spectral region 7.8–15.3 µm [28] – referred to as an atmospheric window due to the relative transparency of the atmosphere within this region.[29] The strength of CFC bands and the unique susceptibility of the atmosphere, at which the compound absorbs and emits radiation, are two factors that contribute to CFCs' "super" greenhouse effect.[30] Another such factor is the low concentration of the compound. Because CO2 is close to saturation with high concentrations,[clarification needed] it takes more of the substance to enhance the greenhouse effect. Conversely, the low concentration of CFCs allow their effects to increase linearly with mass.[30]
Tracer of ocean circulation[edit]
Because the time history of CFC concentrations in the atmosphere is relatively well known, they have provided an important constraint on ocean circulation. CFCs dissolve in seawater at the ocean surface and are subsequently transported into the ocean interior. Because CFCs are inert, their concentration in the ocean interior reflects simply the convolution of their atmospheric time evolution and ocean circulation and mixing.
CFC and SF6 tracer-derived age of ocean water[edit]
Chlorofluorocarbons (CFCs) are anthropogenic compounds that have been released into the atmosphere since the 1930s in various applications such as in air-conditioning, refrigeration, blowing agents in foams, insulations and packing materials, propellants in aerosol cans, and as solvents.[31] The entry of CFCs into the ocean makes them extremely useful as transient tracers to estimate rates and pathways of ocean circulation and mixing processes.[32] However, due to production restrictions of CFCs in the 1980s, atmospheric concentrations of CFC-11 and CFC-12 has stopped increasing, and the CFC-11 to CFC-12 ratio in the atmosphere have been steadily decreasing, making water dating of water masses more problematic.[32] Incidentally, production and release of sulfur hexafluoride (SF6) have rapidly increased in the atmosphere since the 1970s.[32] Similar to CFCs, SF6 is also an inert gas and is not affected by oceanic chemical or biological activities.[33] Thus, using CFCs in concert with SF6 as a tracer resolves the water dating issues due to decreased CFC concentrations.
Using CFCs or SF6 as a tracer of ocean circulation allows for the derivation of rates for ocean processes due to the time-dependent source function. The elapsed time since a subsurface water mass was last in contact with the atmosphere is the tracer-derived age.[34] Estimates of age can be derived based on the partial pressure of an individual compound and the ratio of the partial pressure of CFCs to each other (or SF6).[34]
Partial pressure and ratio dating techniques[edit]
The age of a water parcel can be estimated by the CFC partial pressure (pCFC) age or SF6 partial pressure (pSF6) age. The pCFC age of a water sample is defined as:
p C F C = [ C F C ] F ( T , S ) {\displaystyle pCFC={\frac {[CFC]}{F(T,S)}}}
where [CFC] is the measured CFC concentration (pmol kg−1) and F is the solubility of CFC gas in seawater as a function of temperature and salinity.[35] The CFC partial pressure is expressed in units of 10–12 atmospheres or parts-per-trillion (ppt).[36] The solubility measurements of CFC-11 and CFC-12 have been previously measured by Warner and Weiss[36] Additionally, the solubility measurement of CFC-113 was measured by Bu and Warner[37] and SF6 by Wanninkhof et al.[38] and Bullister et al.[39] Theses authors mentioned above have expressed the solubility, F, at a total pressure of 1 atm as:
ln  F = a 1 + a 2 ( 100 T ) + a 3 ln  ( T 100 ) + a 4 ( T 100 ) 2 + S [ b 1 + b 2 ( T 100 ) + b 3 ( T 100 ) ] {\displaystyle \ln F=a_{1}+a_{2}\left({\frac {100}{T}}\right)+a_{3}\ln \left({\frac {T}{100}}\right)+a_{4}\left({\frac {T}{100}}\right)^{2}+S\left[b_{1}+b_{2}\left({\frac {T}{100}}\right)+b_{3}\left({\frac {T}{100}}\right)\right]}
where F = solubility expressed in either mol l−1 or mol kg−1 atm−1, T = absolute temperature, S = salinity in parts per thousand (ppt), a1, a2, a3, b1, b2, and b3 are constants to be determined from the least squares fit to the solubility measurements.[37] This equation is derived from the integrated Van 't Hoff equation and the logarithmic Setchenow salinity dependence.[37]
It can be noted that the solubility of CFCs increase with decreasing temperature at approximately 1% per degree Celsius.[34]
Once the partial pressure of the CFC (or SF6) is derived, it is then compared to the atmospheric time histories for CFC-11, CFC-12, or SF6 in which the pCFC directly corresponds to the year with the same. The difference between the corresponding date and the collection date of the seawater sample is the average age for the water parcel.[34] The age of a parcel of water can also be calculated using the ratio of two CFC partial pressures or the ratio of the SF6 partial pressure to a CFC partial pressure.[34]
Safety[edit]
According to their material safety data sheets, CFCs and HCFCs are colorless, volatile, toxic liquids and gases with a faintly sweet ethereal odor. Overexposure at concentrations of 11% or more may cause dizziness, loss of concentration, central nervous system depression and/or cardiac arrhythmia. Vapors displace air and can cause asphyxiation in confined spaces. Although non-flammable, their combustion products include hydrofluoric acid, and related species.[40] Normal occupational exposure is rated at 0.07% and does not pose any serious health risks.[41]
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External links[edit]
Gas conversion table
Nomenclature FAQ
Numbering scheme for Ozone-Depleting Substances and their substitutes
Class I Ozone-Depleting Substances
Class II Ozone-Depleting Substances (HCFCs)
CFC illegal trade
History of halon-use by the US Navy
Ozone Loss: The Chemical Culprits
Process using pyrolysis in an ultra high temperature plasma arc, for the elimination of CFCs
[1] Environmental Investigation Agency: Reports etc. on illegal trade and solutions
[2] Environmental Investigation Agency in the USA: Reports etc. on illegal trade and solutions
Freon in car A/C
[3] Phasing out halons in extinguishers
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Halomethanes
Monosubstituted
CH3F
CH3Cl
CH3Br
CH3I
Disubstituted
CH2F2
CH2ClF
CH2BrF
CH2FI
CH2Cl2
CH2BrCl
CH2ClI
CH2Br2
CH2BrI
CH2I2
Trisubstituted
CHF3
CHClF2
CHBrF2
CHF2I
CHCl2F
C*HBrClF
C*HClFI
CHBr2F
C*HBrFI
CHFI2
CHCl3
CHBrCl2
CHCl2I
CHBr2Cl
C*HBrClI
CHClI2
CHBr3
CHBr2I
CHBrI2
CHI3
Tetrasubstituted
CF4
CClF3
CBrF3
CF3I
CCl2F2
CBrClF2
CClF2I
CBr2F2
CBrF2I
CF2I2
CCl3F
CBrCl2F
CCl2FI
CBr2ClF
C*BrClFI
CClFI2
CBr3F
CBr2FI
CBrFI2
CFI3
CCl4
CBrCl3
CCl3I
CBr2Cl2
CBrCl2I
CCl2I2
CBr3Cl
CBr2ClI
CBrClI2
CClI3
CBr4
CBr3I
CBr2I2
CBrI3
CI4
CAt4
* Chiral compound.
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