Six bogies of the Gorakhpur-bound Gorakhdham Express train were damaged in the accident which occurred at around 10.35 AM near Churaib railway station, railway officials and district administration said.
Preliminary reports said fractured rails could be the cause of the accident, according to railway sources.
"As many as 14 passengers were killed in the accident and the number of injured is 95, some of whom some are in serious condition," police said.
However, the UP Home Department said in a statement in Lucknow that at least 40 people were feared killed in the accident.
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Rescue workers struggled to extricate the passengers trapped in the mangled bogies which had overturned following the collision. Paramilitary personnel were called in to assist in the operations.
An inquiry by Commissioner of Railway Safety North East Circle P K Bajpayee has been ordered, Chairman Railway Board Arunendra Kumar said, adding, the exact cause of the accident will be ascertained only after it is completed.
Six bogies-- AC-I and AC-II and four general coaches-- were affected in the accident, he said, adding rescue operations were continuing late in the night.
Rail driver Lakshmi Narayan Singh and guard R K Chauhan were injured and admitted to a hospital. However, assistant loco-pilot Kumar Ravi Ranjan was missing, the CPRO said.
Rail traffic between Delhi and Gorakhpur was hit and a number of trains diverted, railway officials said.
President Pranab Mukherjee, Prime Minister Narendra Modi, Congress Chief Sonia Gandhi and other leaders expressed grief over the loss of lives.
Railways has declared compensation of Rs one lakh to the next of the kin of dead and Rs 50,000 for those who sustained grievous injuries, besides Rs 10,000 to passengers who suffered minor injuries.
The state government has announced free treatment to the injured and hospitals have been put on alert.
Sant Kabir Nagar is about 242 km from Uttar Pradesh capital Lucknow and over 700 km from national capital Delhi.
Emergency helpline numbers in Delhi and Gorakhpur have been activated.